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Manuscript_9b12b98ddcccf4e30fd70e601a811057

α-LiSiH3 α-NaSiH3 α-KSiH3 α-RbSiH3 α-CsSiH3

LiSi NaSi KSi RbSi CsSi

Li Na K Rb Cs Si H

© 2017 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
 Alkali metal silanides α-MSiH3: A family of complex
hydrides for solid-state hydrogen storage
a∗
J. Zhang , S. Yan a, H. Qu a, X.F. Yu a, P. Peng b

a
Hunan Provincial Key Laboratory of Safety Design and Reliability Technology for Engineering

Vehicle, Changsha University of Science and Technology, Changsha 410114, China

b
College of Materials Science and Engineering, Hunan University, Changsha 410082, China

ABSTRACT

The alkali metal silanides α-MSiH3 appear to be a promising family of complex hydrides for

solid-state hydrogen storage. Herein the structural, energetic and electronic properties of α-MSiH3

silanides (M=Li, Na, K, Rb, Cs) and MSi Zintl phases are systematically investigated for the first

time by using first-principles calculations method based on density functional theory. The

structural parameters of α-MSiH3 and MSi including lattice constants and atomic positions are

determined through geometry optimization. The obtained results are close to the experimental data

analysed from X-ray and neutron powder diffraction. The calulations of formation enthalpy show

that α-KSiH3, α-RbSiH3 and α-CsSiH3 silanides are easier to be synthetized relative to α-LiSiH3

and α-NaSiH3, which interprets well the lower thermostabilities of experimental α-LiSiH3 and

α-NaSiH3. Nevertheless, LiSi, KSi and CsSi phases are easier to be formed relative to NaSi and

RbSi. The calculations of hydrogen desorption enthalpy reveal that the dehydrogenation abilities

of α-MSiH3 silanides along the decomposition path of α-MSiH3→MSi+H2 are gradually enhanced

in the order of α-CsSiH3, α-RbSiH3, α-KSiH3, α-NaSiH3 and α-LiSiH3, which may be originated

∗
Corresponding author.
E-mail address: [email protected] (J. Zhang).
.

1
from their decreasing thermostabilities. From a comprehensive point of view including hydrogen

storage capacity, thermostability and dehydrogenation ability, α-KSiH3 (~4.29wt%) is identified

as the most promising alkali metal silanide for reversible hydrogen storage. Analysis of electronic

structures indicates that a significant charge transfer leads to positively charged M ions and

negatively charged SiH3 complex, which constitutes the ionic bonding between them. The bonding

within SiH3 complex not only involves the covalent hybridization between Si (3s)(3p) and H (1s)

orbitals, but also exhibits some ionic bond characteristics due to the partial charge transfer from Si

to H. The covalent bonding interactions between H and Si atoms within SiH3 mainly dominate the

thermostabilities and dehydrogenation properties of α-MSiH3 silanides.

Keywords: Alkali metal silanides; Hydrogen storage materials; First-principles calculations;

Formation enthalpy; Hydrogen desorption enthalpy; Electronic structure

Introduction

Hydrogen is as an ideal energy carrier for the fuel cell applications including

stationary, mobile and portable power applications. The safe, effective and affordable

hydrogen storage is a key challenge in developing hydrogen economy [1]. Solid

materials-based hydrogen storage through reversible formation of hydrides is one of

the most promising methods due to their unique safety and high energy densities

compared to pressurised gasesous and cryogenically liquefied hydrogen [2, 3]. In the

past few decades, a variety of solid-state hydrogen storage materials have been

explored and developed. Among these materials, the light metal hydrides and complex

metal hydrides are considered to be the suitable hydrogen storage media for their high

volumetric and gravimetric hydrogen capacities. For example, MgH2 and LiBH4 are

2
the two typical representatives, which are widely researched for their high hydrogen

storage densities (7.6wt%/110kg·m-3 for MgH2 and 18.5wt%/121kg·m-3 for LiBH4)

[4-6]. However, these hydrides are always suffering from high temperature

requirement, slow kinetics and irreversibility. Although several progresses have been

achieved in enhancing the hydrogen storage performance of metal hydrides by

alloying, nanoscaling, catalyzing, or compositing, the synergetic improvement in the

operating temperature, reversibility and cyclic stability is barely satisfactory [7].

Recently, some multielement alloys or their hydrides such as M-Be-H (M=Li, Na)

[8], Zr-Fe-V [9], RE-Mg-Ni (RE= Rare Metals) [10, 11], Nb4M0.9Si1.1(M=Co, Ni) [12]

have been investigated as the hydrogen storage or negative electrode materials of

nickel-metal hydride (Ni/MH) batteries. In particular, the alkali metal silanides

α-MSiH3 (M=Li, Na, K, Rb, Cs) and MSi Zintl phases are paid increasing attention

for their reversible hydrogen storage capability near ambient conditions [13-20]. The

excellent thermodynamic characteristics of α-MSiH3 silanides originate from their

low entropy variation [13]. For example, α-KSiH3 has been reported as a promising

hydrogen storage material. It has high hydrogen storage capacity of 4.3wt% and

reasonable formation enthapy ∆H=-28kJ/mol·H2, which allows hydrogen sorption at

100 [14-16]. Moreover, α-KSiH3 can be synthesized by direct solid-gas reaction

between KSi Zintl phase and hydrogen. Similar to α-KSiH3, α-RbSiH3 and α-CsSiH3,

with relatively lower hydrogen storage densities of 2.59wt% and 1.83wt%, have been

reported to be cubic isolated solid-state phases and they can also be synthesized

through direct hydrogenation of RbSi and CsSi Zintl phases [17]. Different from the

3
three silanides above, α-LiSiH3 and α-NaSiH3, with relatively higher hydrogen

storage densities of 7.89wt% and 5.56wt%, present the lower thermostability. They

are difficult to be synthesized by the direct hydrogenation of NaSi and LiSi. Some

studies have shown that NaSi disproportionates to NaH and Na8Si46 clathrate phase,

and LiSi forms LiH and Si under hydrogen pressure [18, 20]. Thus, the stabilization of

α-LiSiH3 and α-NaSiH3 with high hydrogen storage densities is still a great challenge.

Although the alkali metal silanides α-MSiH3 are proposed as a promising

family of hydrogen storage materials, their formation abilities, thermostabilities and

dehydrogenation properties have not been studied yet from an energy point of view.

Moreover, the detailed structural parameters of α-MSiH3 and the complicated bonding

characteristics within silanides have not been well investigated due to the difficulty in

determining hydrogen atomic positions by using experimental methods. In this work,

first-principles calculations method based on density functional theory is employed to

conduct a comprehensive study on the structural, energetic and electronic properties

of α-MSiH3 silanides and MSi Zintl phases (M=Li, Na, K, Rb, Cs) for the first time.

The results will contribute to understanding the formation abilities, thermostabilities

and dehydrogenation properties of α-MSiH3 silanides. Furthermore, some underlying

mechanisms associated with the thermostabilities and dehydrogenation properties

are also explored from the perspective of electronic structures, which are expected to

be the theoretical guidances for designing high performance α-MSiH3 complex

hydrides for solid-state hydrogen storage.

Computational models and method

4
 At room temperature, the alkali metal silanides α-MSiH3 (M= Li, Na, K, Rb, Cs)

exhibit the cubic NaCl-type arrangement of alkali metal M and Si atoms with the

space group of Fm-3m, as shown in Fig. 1 [13]. The pyramidal SiH3 complexes are

distributed in random orientations in the crystal structure. The unit cell of each

silanide all contains 4 formula units and the M, Si and H atoms are located at the 4c,

4c and 96k sites, respectively [17]. Their experimental structural parameters including

lattice constants and atomic positions are listed in Table 1. Due to the difficulty in

synthesizing LiSiH3 and NaSiH3 and the lackage of their structural parameters, the

unit cells of LiSiH3 and NaSiH3 are both constructed by adopting the structural data of

KSiH3.

After dehydrogenation of α-MSiH3 along the decomposition path of

α-MSiH3→MSi+H2, the obtained MSi Zintl phases exhibit different crystal structures

from α-MSiH3. For LiSi phase, it presents a tetragonal structure with the space of

I41/a [21]. Its unit cell contains 16 formula units and the Li and Si atoms are located

at the 16f and 16f sites, respectively. For NaSi phase, it has a monoclinic structure

with the space of C2/c. Its unit cell also contains 16 formula units and two different

kinds of Na and Si atoms are located at the 8f (Na1 and Na2) and 8f (Si1 and Si2) sites,

respectively. For MSi (M=K, Rb, Cs) phases, they all belong to the cubic structure

with the space group of P-43n [22]. Their unit cells all contain 32 formula units.

Similar to NaSi phase, there are also two different kinds of M (M=K, Rb, Cs) and Si

atoms which are located at the 8e (M1), 24i(M2), 8e (Si1) and 24i (Si2) sites,

respectively. The experimental structural parameters of MSi Zintl phases are also

5
listed in Table 1.

In this work, all calculations are performed using first-principles plane-wave

pseudopotential method through the CASTEP software package [23]. Ultrasoft

pseudopotentials [24] in reciprocal space are used for the core-valence interactions.

The generalized gradient approximation (GGA) in Perdew-Burke-Ernzerhof (PBE)

format [25] is adopted as the exchange-correction functional. The plane wave cutoff

energy with 500eV and k sampling with different k-point mesh (see Table 1) in

Brillouin zone [26] are employed for the geometry relaxation and electronic structures

calculations of α-MSiH3 silanides and MSi Zintl phases. The pseudo atomic orbitals

used are H 1s1, Si 3s23p2, Li 1s22s1, Na 2s22p63s1, K 3s23p64s1, Rb 4s24p65s1 and Cs

5s25p66s1, repectively. The convergence criteria for energy, force, stress and

displacement are 1.0×10-5eV/atom, 0.03eV/Å, 0.05GPa and 0.001Å, respectively.

Results and discussion

Structural parameter

To examine the accuracy of computational parameters selected in this work,

some testing calculations on the structural parameters of solid bcc-Li, bcc-Na, bcc-K,

bcc-Rb, bcc-Cs, fcc-Si and gaseous H2 are performed. The calculated results are listed

in Table 2. It can be seen that the equilibrium lattice constants of solid elements and

bond length of H2 molecule are in good agreement with experimantal data [27, 28].

The maximum deviation is only 1.59% (a value of bcc-Li), suggesting that the present

calculations are precise enough to represent the ground-state properties of α-MSiH3

silanides and MSi Zintl phases.

6
Formation enthalpy

The formation enthalpy is an important thermodynamic parameter of materials

[29]. It is the best aid to establish whether theoretically predicted phases are likely to

form and be stable, and such data may also serve as guidances for possible synthesis

routes of materials. Commonly, the formation enthalpy is always negative, and the

lower enthalpy value will correspond to the stronger formation ability and the high

thermostability of synthesized materials. In order to investigate the formation ability

and thermostability of α-MSiH3 silanides and MSi Zintl phases, their formation

enthalpies ∆H form are calculated by using Eqs. (1) and (2), respectively [30],

3
∆H form (α − MSiH 3 ) = Etot (α − MSiH 3 ) − Etot
solid
( M ) − Etot
solid
( Si) − Etot ( H 2 ) (1)
2

∆H form ( MSi) = Etot ( MSi) − Etotsolid ( M ) − Etotsolid ( Si) (2)

Where Etot (α − MSiH 3 ) and Etot ( MSi ) are the total energies per formular unit of

solid solid
α-MSiH3 silanides and MSi Zintl phases, respectively. Etot (M ) and Etot (Si ) are

the total energies per formular unit of solid M alkali metals and Si, respectively.

Etot ( H 2 ) refers to the total energy of single gasous H2 molecule. The calculated

formation enthalpies of α-MSiH3 and MSi are plotted in Fig. 2. It can be seen that

these enthalpy values are all negative, meaning structural stabilities of α-MSiH3 and

MSi from a thermodynamics point of view. For α-MSiH3 silanides as shown in Fig.

2(a), their enthalpy values become gradually negative in the order of α-LiSiH3,

α-NaSiH3, α-KSiH3, α-RbSiH3 and α-CsSiH3, suggesting the increasing

thermostability. Comparatively, the values of α-KSiH3, α-RbSiH3 and α-CsSiH3 are

much lower that those of α-LiSiH3 and α-NaSiH3, which indicates that α-KSiH3,

7
α-RbSiH3 and α-CsSiH3 are easier to be synthetized and more stable relative to the

other two silanides. The higher formation enthalpies of α-LiSiH3 and α-NaSiH3

calculated here interpret well the the lower thermostabilities and difficulty in

synthesizing the two silanides reported by previous experiments [18, 20]. As for MSi

Zintl phases, the change of enthalpy values are different from that of α-MSiH3

silanides, as shown in Fig. 2(b). It can be found that the formation enthalpies of MSi

become gradually negative in the order of NaSi, RbSi, LiSi, CsSi and KSi. Apparently,

LiSi, KSi and CsSi phases are easier to be formed relative to NaSi and RbSi. By

contrast, KSi is the most stable Zintl phase with the lowest formation enthalpy of

-16.8937kJ/mol per formular unit.

Hydrogen desorption enthalpy

Similar to the formation enthalpy, the hydrogen desorption enthalpy is also an

important thermodynamic parameter used to identify and classify hydrogen storage

materials. It determines the heat of the overall dehydrogenation reaction of hydrogen

storage materials, which in turn affects their dehydrogenation temperature [31]. In

order to evaluate the dehydrogenation abilities of α-MSiH3 silanides, their hydrogen

desorption enthalpies ∆H des are further calculated by using Eq. (3) [32],

3
∆H des (α − MSiH 3 ) = Etot ( MSi) + Etot ( H 2 ) − Etot ( MSiH 3 ) (3)
2

Where the implications of Etot ( MSiH 3 ) , Etot (MSi ) and Etot ( H 2 ) are the same as

those in Eqs. (1) and (2) above. The calculated results are plotted in Fig. 3(a).

Evidently, the enthalies values are all positive, suggesting the endothermic process for

the dehydrogenation of each silanide. Notablely, the hydrogen desorption enthalpy of

8
α-KSiH3 is calculated as 28.9729kJ/mol·H2, which is very close to the experimental

(22.6kJ/mol·H2) and calculated data (28.1kJ/mol·H2) reported by Chotard et al. [16].

According to the Van’t Hoff equation ln( pHeq / pH0 ) = −(∆H 0 / RT ) + (∆S 0 / R ) [33], it
2 2

can be deduced that the dehydrogenation temperture T of hydrogen storage materials

at a given hydrogen equlibrium pressure pHeq2 exhibits a linear relationship with the

hydrogen desorption enthalpy ∆H 0 . Namely, the less hydrogen desorption enthalpy

will correspond to the lower dehydrogenation temperature of hydrogen storage

materials. Thus, the dehydrogenation temperature of α-MSiH3 silanides is gradually

decreased in the order of α-CsSiH3, α-RbSiH3, α-KSiH3, α-NaSiH3 and α-LiSiH3.

Although α-LiSiH3 and α-NaSiH3 can theoretically dehydrogenate at a relatively

lower temperature, the two silanides have been reported to be difficult to form due to

the disproportionation of LiSi and NaSi when hydrogenation [18, 20]. Therefore,

α-KSiH3 should be the most promising alkali metal silanide for reversible hydrogen

storage by comprehensively considering its hydrogen storage capacity (4.29wt%, see

Fig. 3(b)), thermostability and dehydrogenation ability.

Electronic structure

Density of states

To disclose the bonding characteristics within α-MSiH3 silanides and understand

their thermostabilities and dehydrogenation properties, the total and partial densities

of states of each silanide are calculated and plotted in Fig. 4(a)~(e), respectively. In

these figures, the Fermi level (EF) is set as zero and used as a reference. It can be seen

that these silanides all exhibit the semiconducting behaviors due to the discontinuities

9
of total densities of states near EF with the energy gap less than 4eV. The obvious Si

(3s), Si (3p) and H(1s) orbitals hybridizing in the valence band below EF can be seen,

which contributes the strong covalent bonding interactions between Si and H atoms.

There is hardly any valence oribitals hybridizing between M and Si/H atoms below EF

for α-MSiH3 silanides except for α-CsSiH3, meaning the main ionic bonding

interactions between M and SiH3 complex. As far as α-CsSiH3 is concerned, the Cs

(5p), Si (3s) and H (1s) orbitals hybridizing in the energy range between -10eV and

-7eV can be observed as shown in Fig. 4(e), revealing some covalent bonding

interactions between Cs and SiH3 apart from the ionic bonding ones. The total

densities of states of five α-MSiH3 silanides are further compared as shown in Fig.

4(f). It can be seen that there are three main bonding peaks below EF which originate

from the simultaneous contributions of Si and H valence oribitals for each silanide. It

is notable that the heights of the three bonding peaks are gradually increased in the

order of α-LiSiH3, α-NaSiH3, α-KSiH3, α-RbSiH3 and α-CsSiH3, which is just

consistent with the change order of the formation enthalpies and hydrogen desorption

enthalpies of five α-MSiH3 silanides, as shown in Fig. 2(a) and Fig. 3(a). This

indicates that the thermostabilities and dehydrogenation stabilities of α-MSiH3

silanides are closely associated with the covalent bonding interactions between Si and

H atoms within α-MSiH3. Namely, the weaker convalent bonding interactions

between Si and H will lead to the lower thermostabilities as well as the stronger

dehydrogenation abilities of α-MSiH3 silanides.

Charge density

10
 Further analysis of the charge density distribution of α-MSiH3 silanides and

charge transfer between atoms is performed. Due to the similarity of bonding

characteristics of five α-MSiH3 silanides, α-KSiH3 is taken as an example and its total

charge density ρ(r) and difference charge density ∆ρ(r) are plotted in Fig. 5(a) and (b),

respectivey. The difference charge density ∆ρ(r) is defined as the difference between

the total charge density of the solid and a superposition of atomic charge density with

the same spatial coordinates as in the solid [34]. It can be seen from Fig. 5(a) that the

charges are mainly distributed around the SiH3 complex. There is an obvious

overlapping of electron cloud between Si and H within SiH3 complex, while nearly no

overlapping of electron cloud between K and SiH3 can be observed. This suggests that

there are strong bonding interactions between Si and H, while there are weak ones

between K and SiH3 complex. From Fig. 5(b), it can be also seen that there is a

significant charge transfer leading to K positively and SiH3 units negatively charged,

which results in the ionic bonding interactions between K and SiH3. Within SiH3

complex, it can be also found that there is a partial charge transfer from Si to H,

indicating that, besides the covalent bonding interactions between Si and H, there is

also a certern degree of ionic bonding ones.

Bond order and ionicity

From the anlysis of the density of states and charge density above, it is evident

that the H atoms have a stronger bonding with Si relative to M atoms. In order to

understand well the correlation among the bonding characteristics, thermostabilities

and dehydrogenation properties of α-MSiH3, the bonding interactions between H and

11
Si atoms are further systematically investigated according to the Mulliken population

analysis [35] including the ionicity of each atoms and bond order between atoms

within α-MSiH3. The results are plotted in Fig. 6. From Fig. 6(a), it is apparent that

the ionicities of M atoms are always positive, whereas the ionicities of Si and H atoms

are always negative, meaning the charge transfer from M atoms towards Si and H

atoms. As explained earlier, the bond order is the overlap population of electrons

between atoms, and it is a measure of the strength of covalent bonding between atoms

[36]. Fig. 6(b) shows the bond orders calculated between Si and surrounding H atoms

within α-MSiH3. It is found that the H-Si bond orders are always positive, indicating

that there are strong covalent bonding interactions between Si and H. Also, the

covalent bonding interactions between H and Si within α-KSiH3, α-RbSiH3 and

α-CsSiH3 are relatively stronger than those within α-LiSiH3 and α-NaSiH3. Due to the

characteristics of SiH3 units with mixed ionic-covalent bonds between H and Si atoms,

we further estimate the amount of transferred charges between H and Si atoms by

calculating the ionicity differences ∆I0(I0[H]-I0[Si]) [34], where I0[H] and I0[Si] are

the ionicity of H and Si atoms, respectively. The results are also plotted in Fig. 6(b), It

can be seen that the ∆I0(I0[H]-I0[Si]) in α-KSiH3, α-RbSiH3 and α-CsSiH3 are

relatively lower than those in α-LiSiH3 and α-NaSiH3, suggesting that few charge

transfer from Si to H in α-KSiH3, α-RbSiH3 and α-CsSiH3 relative to the other two

systems. Based on the comprehensive analysis including the bond order, ionicity

differences, formation enthalpy and hydrogen desorption enthalpy, we can conclude

again that the thermostabilities and dehydrogenation properties of α-MSiH3 silanides

12
are mainly dominated by the covalent bonding interactions between H and Si. The

weaker convalent bonding interactions between Si and H will result in the lower

thermostabilities and the stronger dehydrogenation abilities. This conclusion is just

consistent with that induced from densities of states above.

Conclusions

Using first-principles calculations method based on denisty functional theory, the

structural, energetic and electronic properties of α-MSiH3 silanides and MSi Zintl

phases (M=Li, Na, K, Rb, Cs) are systematically investigated for the first time. Some

key conclusions are summarized as the following,

1) The structural parameters of α-MSiH3/MSi including lattice constants and

atomic positions are determined through geometry optimization, which are close to

the expereimental data analysed from X-ray and neutron powder diffraction.

2) α-KSiH3, α-RbSiH3 and α-CsSiH3 silanides are easier to be synthetized

relative to α-LiSiH3 and α-NaSiH3, whereas LiSi, KSi and CsSi Zintl phases are easier

to be formed relative to NaSi and RbS.

3) The dehydrogenation abilities of α-MSiH3 silanides are gradually enhanced in

the order of α-CsSiH3, α-RbSiH3, α-KSiH3, α-NaSiH3 and α-LiSiH3, and α-KSiH3

(~4.29wt%) is approved to be the most promising alkali metal silanide for reversible

hydrogen storage.

4) There mainly exhibit the ionic bonding interactions between M and SiH3

complex in α-MSiH3 silanides. Within SiH3, there are mixed ionic-covalent bonding

interactions between H and Si atoms. The covalent bonding interactions between H

13
and Si atoms mainly dominate the thermostabilities and dehydrogenation properties of

α-MSiH3 silanides.

Acknowledgments

This work was financially supported by the National Natural Science

Foundation of China (No. 51401036), the Hunan Provincial Natural Science

Foundation of China (No.17JJ3086) and the Science Research Project of Hunan

Province Office of Education (No. 16K001).

REFERENCES

[1] Schlapbach L, Züttel A. Hydrogen-storage materials for mobile applications.

Nature 2001; 414: 353-8.

[2] Sakintuna B, Lamari-Darkrim F, Hirscher M. Metal hydride materials for solid

hydrogen storage: A review. Int J Hydrogen Energ 2007; 32: 1121-40.

[3] Zhu M, Wang H, Ouyang LZ, Zeng MQ. Composite structure and hydrogen

storage properties in Mg-based alloys. Int J Hydrogen Energ 2006; 31: 251-7.

[4] Ouyang LZ, Yang XS, Zhu M, Liu JW, Dong HW, Sun DL, Zou J, Yao XD.

Enhanced hydrogen storage kinetics and stability by synergistic effects of in

Situ formed CeH2.73 and Ni in CeH2.73-MgH2-Ni nanocompoistes. J Phys Chem

C 2014; 118: 7808-20.

[5] Sadhasivam T, Kim HT, Jung S, Roh SH, Park JH, Jung HY. Dimensional effects

of nanostructured Mg/MgH2 for hydrogen storage applications: A review.

Renew Sust Energ Rev 2017; 72: 523-34.

[6] Shao J, Xiao XZ, Fan XL, Zhang LT, Li SQ, Ge HW, Wang QD, Chen LX.

14
 Low-temperature reversible hydrogen storage properties of LiBH4: A synergetic

effect of nanoconfinement and nanocatalysis. J Phys Chem C 2014; 118:

11252-60.

[7] Wang H, Lin HJ, Cai WT, Ouyang LZ, Zhu M. Tuning kinetics and

thermodynamics of hydrogen storage in light metal element based systems-A

review of recent progress. J Alloy Compd 2016; 658: 280-300.

[8] Rehmat B, Rafiq MA, Javed Y, Irshad Z, Ahmed N, Mirza SM. Elastic properties

of perovskite-type hydrides LiBeH3 and NaBeH3 for hydrogen storage. Int J

Hydrogen Energ 2017; doi.org/10.1016/j.ijhydene.2017.01.109.

[9] Cao ZJ, Ouyang LZ, Wang H, Liu JW, Sun LX, Felderhoff M, Zhu M.

Development of Zr-Fe-V alloys for hybrid hydrogen storage system. Int J

Hydrogen Energ 2016; 41: 11242-53.

[10] Cao ZJ, Ouyang LZ, Li LL, Lu YS, Wang H, Liu JW, Min D, Chen YW, Xiao

FM, Sun T, Tang RH, Zhu M. Enhanced discharge capacity and cycling

properties in high-samarium, praseodymium/neodymium-free, and low-cobalt

A2B7 electrode materials for nickel-metal hydride battery. Int J Hydrogen Energ

2015; 40: 451-5.

[11] Ouyang LZ, Cao ZJ, Li LL, Wang H, Liu JW, Min D, Chen YW, Xiao FM, Tang

RH, Zhu M. Enhanced high-rate discharge properties of

La11.3Mg6.0Sm7.4Ni61.0Co7.2Al7.1 with added graphene synthesized by plasma

milling. Int J Hydrogen Energ 2014; 39: 12765-72.

[12] Ångström J, Zlotea C, Latroche M, Sahlberg M. Hydrogen-sorption properties of

15
 Nb4M0.9Si1.1 (M=Co, Ni) hydrides. Int J Hydrogen Energ 2015; 40: 2692-7.

[13] Kranak VF, Lin YC, Karlsson M, Mink J, Norberg ST, Häussermann U.

Structural and vibrational properties of Silyl (SiH3-) anion in KSiH3 and RbSiH3:

New insight into Si-H interactions. Inorg Chem 2015; 54: 2300-9.

[14] Jain A, Ichikawa T, Yamaguchi S, Miyaoka H, Kojima Y. Catalytic modification

in dehydrogenation properties of KSiH3. Phys Chem Chem Phys 2014; 16:

26163-7.

[15] Janot R, Tang WS, Clémencon D, Chotard JN. Catalyzed KSiH3 as a reversible

hydrogen storage material. J Mater Chem A 2016; 4: 19045-52.

[16] Chotard JN, Tang WS, Raybaud P, Janot R. Potassium silanide (KSiH3): A

reversible hydrogen storage material. Chem-Eur J 2011; 17: 12302-9.

[17] Tang WS, Chotard JN, Raybaud P, Janot R. Enthalpy-entropy compensation

effect in hydrogen storage materials: Striking example of alkali silanides MSiH3

(M=K, Rb, Cs). J Phys Chem C, 2014; 118: 3409-19.

[18] Tang WS, Chotard JN, Janot R. Synthesis of single-phase LiSi by ball-milling:

Electrochemical behavior and hydrogenation properties. J Electrochem Soc 2013;

160: A1232-40.

[19] Jain A, Miyaoka H, Ichikawa T, Kojima Y. Tailoring the absorption-desorption

properties of KSiH3 compound using nano-metals (Ni, Co, Nb) as catalyst. J

Alloy Compd 2015; 645: S144-7.

[20] Tang WS, Chotard JN, Raybaud P, Janot R. Hydrogenation properties of KSi and

NaSi Zintl phases. Phys Chem Chem Phys, 2012; 14: 13319-24.

16
[21] Evers J, Oehinger G, Sextl G. LiSi, a unique Zintl phase-although stable, it long

evaded synthesis. Eur J of Solid State Inorg Chem 1997; 34: 773-84.

[22] Villars P, Calvert LD. Pearson’s handbook of crystallographic data for

intermetallic phases. Metals Park, Ohio, ASM, 1985.

[23] Segall MD, Lindanp LD, Probert MJ, Pickard CJ, Hasnip PJ, Clark SJ, Payne

MC. First-principles simulation: ideas, illustrations and the CASTEP code. J

Phys: Condens Matter 2002; 14: 2717-44.

[24] Vanderbilt D. Soft self-consistent pseudopotentials in a generalized eigenvalue

formalism. Phys Rev B 1990; 41: 7892-5.

[25] Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made

simple. Phys Rev Lett 1996; 77: 3865-8.

[26] Fischer T, Almlof J. General methods for geometry and wave function

optimization. J Phys Chem 1992; 96: 9768-74.

[27] Kittel C. Introduction to solid state physics, Ch. 13. New York: John Wiley and

Sons, Inc, 1986.

[28] Fukai Y. The metal-hydrogen system. Berlin: Springer-Verleg, 1993.

[29] Takahashi Y, Yukawa H, Morinaga M. Alloying effects on the electronic

structure of Mg2Ni intermetallic hydride. J Alloy Compd 1996; 242: 98-107.

[30] Song Y, Guo ZX. Electronic structure, stability and bonding of the Li-N-H

hydrogen storage system. Phys Rev B 2006; 74: 195120-6.

[31] Zhang J, Huang YN, Peng P, Mao C, Shao YM, Zhou DW. First-principles

study on the dehydrogenation properties and mechanisms of Al-doped

17
 Mg2NiH4. Int J Hydrogen Energ 2011; 36: 5375-82.

[32] van Setten MJ, de Wijs GA, Brocks G. Ab initio study of the effects of

transition metal doping of Mg2NiH4. Phys Rev B 2007; 76: 075125-32.

[33] Zhang J, Zhou YC, Ma ZS, Sun LQ, Peng P. Strain effect on structural and

dehydrogenation properties of MgH2 hydride from first-principle calculations.

Int J Hydrogen Energ 2013; 38: 3661-9.

[34] Peles A, Alford JA, Ma Z, Yang L, Chou MY. First-principles study of NaAlH4

and Na3AlH6 complex hydrides. Phys Rev B 2004; 70: 165105-11.

[35] Mulliken RS. Electronic population analysis on LCAO-MO molecular wave

functions. I. J Chem Phys 1955; 23: 1833-40.

[36] Matumura T, Yukawa H, Morinaga M. Alloying effects on the electronic

structures of VH2 and V2H. J Alloy Compd 1999; 284: 82-8.

18
Figure captions

Fig. 1-The crystal cell models of α-MSiH3 silanides and MSi Zintl phases (M=Li, Na,

K, Rb, Cs).

Fig. 2-The calculated formation enthalpies of α-MSiH3 silanides (a) and MSi Zintl

phases (M=Li, Na, K, Rb, Cs) (b).

Fig. 3-The calculated hydrogen desorption enthalpies (a) and theoretical hydrogen

storage capacities (b) of α-MSiH3 silanides (M=Li, Na, K, Rb, Cs).

Fig. 4-The calculated total and partial densities of states of α-MSiH3 silanides (M=Li,

Na, K, Rb, Cs) (a)~(e) and the comparison of total densities of states (f).

Fig. 5-The calculated valence (a) and difference charge densities (b) of α-KSiH3

silanide.

Fig. 6-The calculated ionicity (a), bond order of H-Si and ionicity difference

∆I0(I0[H]-I0[Si]) (b) of α-MSiH3 silanides (M=Li, Na, K, Rb, Cs).

19
Table 1-The calculated equilibrium lattice constants, atomic positions and total energies per formula unit (f.u.) of α-MSiH3 silanides and MSi Zintl phases

(M=Li, Na, K, Rb, Cs).

Lattice constant (Å) Atomic position Total energy

α-LiSiH3 a=6.5690 - Li (4c): 0, 0, 0 - -345.0022 4×4×4

(Fm-3m, cubic) Si (4c): 0.4698, 0.5192, 0.5012 -

H (96k): 0.4835, 0.6549, 0.7338 -

α-NaSiH3 a=6.7892 - Na (4c):0, 0, 0 - -1459.3143 4×4×4

(Fm-3m, cubic) Si (4c): 0.4653, 0.5296, 0.5116 -

H (96k): 0.5289, 0.6491, 0.7052 -

α-KSiH3 a=7.2008 a=7.2245 a K (4c): 0, 0, 0 K (4c): 0, 0, 0 a -934.7379 3×3×3

(Fm-3m, cubic) Si (4c): 0.4798, 0.5187, 0.4808 Si (4c): 0.5, 0.5, 0.5 a

H (96k): 0.5642, 0.6449, 0.6261 H (96k): 0.5632, 0.6365, 0.6365 a

(Fm-3m, cubic) Si (4c): 0.4807, 0.5169, 0.4824 Si (4c): 0.5, 0.5, 0.5 a

H (96k): 0.5610, 0.6380, 0.6228 H (96k): 0.5616, 0.6327, 0.6327 a

α-CsSiH3 a=7.9462 a=7.8320 a Cs (4c): 0, 0, 0 Cs (4c):0, 0, 0 a -705.2695 3×3×3

(Fm-3m, cubic) Si (4c): 0.4815, 0.5137, 0.4878 Si (4c): 0.5, 0.5, 0.5 a

H (96k): 0.5597, 0.6310, 0.6179 H (96k): 0.5616, 0.6273, 0.6273 a

LiSi a=9.1450 a=9.354 b Li(16f): 0.1350, 0.8903, 0.1309 Li(16f): 0.0810, 0.8860, 0.0602 b -297.4331 3×3×5

(I41/a, c=5.4574 c=5.746 b Si(16f): 0.1472, 0.8862, 0.6049 Si(16f): 0.0111, 0.9522, 0.5937 b

tetragonal)

NaSi a=11.9744 a=12.190 c Na1 (8f): 0.3550, 0.6735, 0.3577 Na1 (8f): 0.351, 0.662, 0.358 c -1411.6314 2×4×3

(C2/c, b=6.5333 b=6.550 c Na2 (8f): 0.6356, 0.9074, 0.4507 Na2 (8f): 0.632, 0.900, 0.455 c

monoclinic) c=11.0178 c=11.180 c Si1 (8f): 0.4355, 0.1944, 0.3115 Si1 (8f): 0.440, 0.210, 0.314 c

β=117.4591° β=119° c Si2 (8f): 0.5959, 0.4524, 0.3571 Si2 (8f): 0.597, 0.463, 0.357 c
 KSi a=13.7119 a=12.620 c K1 (8e): 0.3338, 0.3338, 0.3338 K1 (8e): 0.331, 0.331, 0.331 c -886.7409 2×2×2

(P-43n, cubic) K2 (24i): 0.3373, 0.1398, 0.0662 K2 (24i): 0.336, 0.141, 0.064 c

Si1 (8e): 0.0680, 0.0680, 0.0680 Si1 (8e): 0.068, 0.068, 0.068 c

Si2 (24i): 0.0628, 0.3171, 0.4261 Si2 (24i): 0.063, 0.318, 0.427 c

RbSi a=13.1601 a=13.040 c Rb1 (8e): 0.3327, 0.3327, 0.3327 Rb1 (8e): 0.331, 0.331, 0.331 c -766.6876 2×2×2

(P-43n, cubic) Rb2 (24i): 0.3363, 0.1386, 0.0655 Rb 2 (24i): 0.336, 0.141, 0.004 c

Si1 (8e): 0.0653, 0.0653, 0.0653 Si1 (8e): 0.066, 0.066, 0.066 c

Si2 (24i): 0.0595, 0.3148, 0.4288 Si2 (24i): 0.061, 0.316, 0.429 c

CsSi a=13.7286 a=13.500 c Cs1 (8e): 0.3336, 0.3336, 0.3336 Cs1 (8e): 0.331, 0.331, 0.331 c -657.1339 2×2×2

(P-43n, cubic) Cs2 (24i): 0.3382, 0.1394, 0.0666 Cs 2 (24i): 0.336, 0.141, 0.062 c

Si1 (8e): 0.0625, 0.0625, 0.0625 Si1 (8e): 0.063, 0.063, 0.063 c

Si2 (24i): 0.0583, 0.3115, 0.4322 Si2 (24i): 0.059, 0.315, 0.431 c

a
Reference [17].
b
Reference [21].

c
Reference [22].
Table 2-The calculated equilibrium lattice constants, bond length and total energies per

formula unit (f.u.) of solid bcc-Li, bcc -Na, bcc-K, bcc-Rb, bcc-Cs, fcc-Si and gaseous H2.

Structural parameter (Å) Total energy K-point

bcc-Li a=3.4354 a=3.491 a -189.9765 8×8×8

bcc-Na a=4.1869 a=4.225 a -1304.2709 6×6×6

bcc-K a=5.2745 a=5.225 a -779.2330 6×6×6

bcc-Rb a=5.6543 a=5.585 a -659.2672 4×4×4

bcc-Cs a=6.1400 a=6.045 a -549.6685 4×4×4

fcc-Si a=5.4633 a=5.430 a -107.3328 8×8×8

H2 d=0.7525 d=0.741 b -31.6977 2×2×2

a
Reference [27].

b
Reference [28].
Fig. 1

α-LiSiH3 α-NaSiH3 α-KSiH3 α-RbSiH3 α-CsSiH3

LiSi NaSi KSi RbSi CsSi

Li Na K Rb Cs Si H
Fig. 2

(a) (b)
Fig. 3

(a) (b)
Fig. 4

(a) (b)

(c) (d)

(e) (f)
Fig. 5

(a) (b)
Fig. 6

(a) (b)
 Highlights

> Structural parameters of α-MSiH3 silanides and MSi Zintl phases are determined.

> α-KSiH3, α-RbSiH3 and α-CsSiH3 are easier to be formed than α-LiSiH3 and

α-NaSiH3.

> LiSi, KSi and CsSi are easier to be synthesized than NaSi and RbSi.

> Dehydrogenation ability is enhanced in the order of Cs, Rb, K, Na and Li silanide.

> Covalent bonding between H and Si dominates thermostability of α-MSiH3.