i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2

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First-principles analysis of electrochemical

hydrogen storage behavior for hydrogenated
amorphous silicon thin film in high-capacity
proton battery

Haimin Zhang a,b,c,*, Yongchun Luo a,b,**, Yujie Xiang b, Fuling Tang a,b,
Qiankun Zhang b, Boyang Lin b, Chen Wu b, Xinhui Liu b, Boshi Su b
a
State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou University of
Technology, Lanzhou 730050, People's Republic of China
b
School of Materials Science and Engineering, Lanzhou University of Technology, Lanzhou 730050, People's Republic
of China
c
School of Science, Lanzhou University of Technology, Lanzhou 730050, People's Republic of China

highlights graphical abstract

Reason for improving electro-

chemical performance of electrode
by hydrogenation is explained.

Transformation of a-Si:H electrode
electronic structure during charge/
discharge is clarified.

Mechanisms of hydrogen diffusion
from the surface to the bulk of a-
Si:H electrodes are predicted.

Effect of oxygen surface coverage
on electrochemical hydrogen stor-
age behavior is investigated.

Competitive mechanism between
hydrogen storage and electro-
chemical desorption is revealed.

article info abstract

Article history: Silicon material electrodes as proton carriers for high-capacity proton battery have only
Received 20 December 2022 been proposed for such a short period of time that their physicochemical properties and
Received in revised form electrochemical hydrogen storage behavior during charge and discharge processes remain
8 February 2023 nearly uncharted territory. Herein, the hydrogenated amorphous silicon (a-Si:H) thin film
electrodes are prepared by radio frequency sputtering followed by ex-situ hydrogenation.

* Corresponding author. State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou University of
Technology, Lanzhou 730050, People's Republic of China.
** Corresponding author. State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou University of
Technology, Lanzhou 730050, People's Republic of China.
E-mail addresses: [email protected] (H. Zhang), [email protected] (Y. Luo).
https://doi.org/10.1016/j.ijhydene.2023.03.034
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2 20239

Accepted 5 March 2023 The electrochemical properties of a-Si:H electrodes are tested experimentally, and the
Available online 21 March 2023 electrochemical hydrogen storage behaviors of a-Si:H electrodes are analyzed by first-
principles calculations. The results show that the hydrogenation process significantly in-
Keywords: creases the electrochemical capacity of the electrodes and reduces the band gap of the
Electrochemical properties electrode structure. The electrode exhibits weak conductivity during the initial charging,
Electrochemical hydrogen storage but the instability of the electrode electronic structure during the later charging results in a
behavior slight fluctuation of the electrochemical charging process. The a-Si:H electrode have better
Hydrogen evolution reaction electrochemical hydrogen storage/release reversibility than non-hydrogenated electrodes,
Hydrogen amorphous silicon but this reversibility is weakened by oxygen atoms covered on the electrode surface. The
Proton battery electrochemical hydrogen storage process is easier to accomplish than the electrochemical
desorption process of hydrogen evolution reaction for the a-Si:H electrodes. The a-Si:H thin
film electrode is more stable on the Ni(111) substrate surface and the good conductivity of
the electrode/substrate interface provides convenient conditions for the free transport of
electrons in the electrochemical charge/discharge processes. We believe that these results
perfectly explain the microscopic mechanisms responsible for the electrode reaction and
electrochemical behavior of a-Si:H electrodes in this type of proton battery, and have a
certain reference value in understanding the physicochemical properties and electro-
chemical hydrogen storage behavior of silicon material electrodes applied to other types of
batteries during charge/discharge processes.
© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

[44e46], vanadium oxides [47], ruthenium oxides [48,49], ‘tita-

Introduction nium oxides [50,51], Prussian blue analogs and Turnbull blue
analogs [52e54], as well as organic electrode materials
To alleviate the intolerable burden of carbon emissions on the carbonyl compound [55e57], imine compound [58,59], poly-
environment, it is imperative to vigorously develop sustain- aniline [60,61] and covalent organic frameworks [62,63], for
able energy sources, including solar [1e3], biomass [4,5], novel proton batteries and proton-ion batteries. Besides,
hydrogen [6e10] and other energy conversions and storages inspired by the outstanding performance of silicon material
[11,12]. Proton batteries are hydrogen storage devices that electrodes in lithium-ion batteries and the high theoretical
enable reversible electrochemical conversion of hydrogen hydrogen storage capacity of silicon hydrides [64e66], sporadic
energy into electrical energy. The history of proton batteries research activities have been conducted on silicon electrodes
dates back to the first rechargeable battery, the lead-acid as proton carriers for proton batteries in recent years. Merazga
battery, and subsequent nickel-cadmium and nickel-metal and Honarpazhouh demonstrated an electrochemical
hydride batteries [13e15]. At present, proton batteries have hydrogen storage capacity of 86 and 232 mAh g1 for nano-
attracted extensive attention due to their unique advantages porous silicon thin-film electrodes in an aqueous electrolyte
in terms of satisfying cost effectiveness, high safety and of 3 M H2SO4, respectively [67,68]. The maximum electro-
environmental friendliness [16e19]. Compared with metal chemical hydrogen storage capacity of this electrode can be
ions, such as Naþ, Zn2þ, Al3þ, proton possesses greater abun- substantially increased to 546.1 mAh g1 by coating them with
dance, lower molar mass, smaller ionic size and higher ionic palladium and graphene oxides [68], and to 537 mAh g1 by
conductivity [20e24]. Clearly, the reserve on Earth determines decorating them with palladium and carbon nanotubes [69].
the cost, low molar mass tends to correspond to higher Also, Young and coworkers investigated the electrochemical
theoretical capacity, small ionic size usually implies better performance of hydrogenated amorphous silicon (a-Si:H) thin-
cycle life, and ionic conductivity generally affects the kinetic film electrodes deposited by chemical vapor deposition in an
property [15,25e27]. As a proton carrier, the ideal electrode anhydrous ionic liquid electrolyte of 1-ethyl-3-
material should satisfy the requirements of excellent rate methylimidazolium acetate ([EMIM][Ac]) mixed with 2 M
performance, high theoretical capacity, good chemical sta- glacial acetic acid (CH3COOH, ac) [70]. Impressively, this elec-
bility, pollution-free, nontoxicity, and a wide operating trode delivers an ultrahigh electrochemical discharge capacity
voltage window [14,28e30]. of 3635 mAh g1 at a charge capacity of 5752 mAh g1, and the
To date, the research on proton carriers can be divided into electrochemical capacity of amorphous silicon (a-Si) electrode
two main branches, one is to continuously improve and perfect prepared by physical vapor deposition can be significantly
the hydrogen storage alloys, including AB5 type [31e33], AB2 increased from less than 200 mAh g1 to 2377 mAh g1 by ex-
type [34e36], solid solution [37e39], superlattice structure situ hydrogenation. Undoubtedly, the extraordinary electro-
[40e42] and layered structure hydrogen storage alloys [43], to chemical hydrogen storage capacity of a-Si:H electrodes pro-
solve the problems such as self-discharge and electrode pul- vides a huge imaginative and creative space for the potential
verization in nickel-metal hydride batteries, and the other is to future applications of proton batteries, and the wider electro-
persistently explore and develop new electrode materials, chemical window and lower limiting operating temperature of
such as inorganic electrode materials manganese oxides ionic liquid electrolytes compared to aqueous electrolytes also
20240 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2

offer more possibilities for further improving the energy den- monocrystalline silicon target with resistivity of less than
sity of proton battery and extending its applicable temperature 0.001 U cm was employed to the sputter deposition source. The
range. Nevertheless, silicon material electrodes for proton target-substrate distance of 75 mm was maintained. To prevent
batteries have only been proposed for such a short period of the film electrodes deposited on the smooth Ni substrate from
time that their physicochemical properties and electro- partially shedding during hydrogenation and to increase the
chemical hydrogen storage behavior during charge and bonding strength between the film electrodes and the substrate,
discharge remain nearly uncharted territory. the Ni substrate surface was sandblasted prior to deposition to
In our previous work, we have experimentally demon- increase surface roughness. The sputter deposition parame-
strated that the hydrogen content of the a-Si:H electrode in- ters, including 300 W RF power, 50 V reverse bias voltage and
creases significantly with increasing hydrogenation 15 min deposition time, were performed at the operating pres-
temperature, which is the dominant factor responsible for the sure of 0.5 Pa with 99.9999% pure Ar gas. The gas-solid reaction
dramatic increase in the electrochemical discharge capacity is used to hydrogenate these as-deposited thin-film electrodes
of this electrode, despite the fact that the higher hydrogena- in a steel reactor at a pressure of 1 MPa and a temperature of 200,
tion temperature partially and slightly crystallizes the elec- 300 or 500  C for 2h in 99.999% pure H2 gas.
trode and the residual oxygen in the high purity hydrogen gas
(99.999%) partially oxidates its surface [71]. From the subse- Materials characterization
quent theoretical calculations, it has been found that the
electronic properties of the a-Si:H electrodes are very closely The mass of the a-Si:H thin-film electrodes were measured
related to the hydrogen content of their structures, and that using an electron analytical balance (MS105DU, Mettler
the unstable transition state structures tend to have good Toledo), and the thickness of electrodes was measured using a
electrical conductivity [72], which is favorable for charge surface profiler (MicroXAM-800, KLA-Tencor) and field emis-
transfer in the electrodes, enhancement of the charge- sion scanning electron microscope (SEM, JSM6700F, JEOL). The
discharge rate, and reduction of the electrode polarization. structure of electrods was determined by XRD (Empyrean,
However, the above results are still insufficient to fully un- Malvern Panalytical) and Fourier transform laser Raman
derstand the electrochemical hydrogen storage behavior, spectroscopy (Raman, Raman 950, Nicolet), while the sample
such as the hydrogen diffusion mechanism near the electrode composition and bonding configurations were analyzed by
surface, the hydrogen evolution reaction at the electrode- XPS (AXIS Supra, Kratos) and FTIR (Nicolet IS5, Thermo
electrolyte interface, and the hydrogen storage mechanism Scientific).
in the bulk of the electrode, for this novel proton battery.
Herein, the a-Si:H electrodes are prepared by radio fre- Electrochemical measurement
quency (RF) magnetron sputtering technique followed by ex-
situ hydrogenation, and their structure, composition and The electrochemical charge/discharge and cycle measure-
bonding configurations are determined by a combination of X- ments for the a-Si:H thin-film electrodes were performed with
ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) a Swagelok half-cell (Fig. S1a in the Supporting Information)
and Fourier transform infrared spectrometer (FTIR). The a- using a HYD-B-5V/500 mA battery program control tester at
Si:H structure consistent with the experimentally dominant constant currents. It has a charging capacity of 4000 mAh g-1,
bond configuration was chosen as the prototype and the a charging rate of 0.5C, a discharge rate of 0.05C, and a cutoff
density functional theory (DTF) based first-principles calcu- voltage of 0.6 V. Cyclic voltammetry (CV) was performed using
lations are employed to reveal the variation law of the elec- a CH1660D electrochemical workstation and an Ag/AgCl
tronic structure of a-Si:H electrodes as the hydrogen content reference electrode (þ0.2 V vs. SHE) in a three-electrode
changes during charge/discharge and the hydrogen absorp- Swagelok cell (Fig. S1b in the Supporting Information). The
tion capability of electrode structure with different hydrogen range of potential scanning was 1.8e0.2 V and the speed of
content in this process. Furthermore, we predicted the energy potential scanning was 50 mV/s.
barrier that hydrogen must surpassed to be transferred from
the electrode surface to the bulk, explored the effect of surface Computational details
oxygen coverage on the electrode hydrogen absorption capa-
bility, evaluated the competing mechanisms of hydrogen The DFT calculations were performed using the Vienna Ab-
diffusion and hydrogen evolution reaction (HER) at the elec- initio Simulation Package (VASP) code [73e75]. The
trode surface, and investigated the electronic structure of the projector-augmented-wave (PAW) [76,77] pseudopotentials
electrode/substrate interface and the tendency of silicon were used to approximate the ion-electron interactions and
atoms to form thin films on different Ni crystal faces. the Perdew-Burke-Ernzerhof (PBE) [78e80] functional within
the generalized gradient approximation (GGA) [81e83] was
used to describe the electron-electron exchange correlations.
Experimental section In order to more accurately reflect the physicochemical
properties of the electrodes in different electrochemical
Electrode materials states, we choose the a-Si:H structure consistent with the
dominant bond configuration in the experiment as a proto-
The a-Si:H thin-film electrodes of about 200 nm thickness were type to design and construct electrode structure models in
prepared on nickel substrates by RF magnetron sputtering fol- various electrochemical states including the structures with
lowed by ex-situ hydrogenation. A boron-doped different hydrogen content, supercell model and slab models.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2 20241

All structures and models are finely optimized. The plane- thickness is about 200 nm (Fig. S2 in the Supporting Infor-
wave energy cutoff was set to 400 eV and the k-point mesh of mation). Based on the XRD pattern shown in Fig. 1c, it can be
5  5  5, 3  3  3 and 5  5  1 was used to optimize these found that the film thickness is so thin that the X-ray incident
structures, supercell and slab models, respectively. A denser at a small angle can still penetrate the film to the substrate. No
k-point grid for each structure model was used for the corre- distinct characteristic peak belonging to crystalline Si is found
sponding electronic properties calculations. The Born- in the XRD pattern, but only an obscure wave-packet is pre-
Oppenheimer molecular dynamics (MD) simulations [84,85] sent near this position, indicating that these prepared a-Si:H
implemented in the VASP code were performed using super- electrodes have an amorphous structure, which can be further
cells of more than 100 atoms. The climbing image nudged confirmed by the Raman spectroscopy results shown in
elastic band method (CI-NEB) [86,87] with VASP as the Fig. 1d.
computational engine was used to determine the diffusion To further confirm the electrode structure, the wave packet
energy barrier. region in the XRD pattern is enlarged and shown in Fig. 1e. It
can be found that the center position of the wave packet cor-
responds to the characteristic peak of crystalline silicon, while
Results and discussion the peak position of the wave packet corresponds to the posi-
tion of the strongest peak of the XRD simulated by the struc-
Electrode characterization ture in Fig. 1b, which indicates that hydrogenation may lead to
the peak of the wave packet to move in the direction of small
The a-Si thin films were deposited on Ni substrates by RF angles. Fig. 1f shows the FTIR spectra of the a-Si:H electrodes
magnetron sputtering and then hydrogenated for 2h at a hydrogenated at different hydrogenation temperature, whose
hydrogen pressure of 1 MPa and at temperatures of 200  C, vibration modes mainly include the Si-Si stretching mode
300  C or 500  C to obtain the a-Si:H thin film electrodes with (610 cm1), Si-H wagging mode (640 cm1) and stretching mode
different hydrogenation conditions. A schematic illustration (2000 cm1), Si-H2 bending mode (880 cm1) and Si-O wagging
of the preparation process is presented in Fig. 1a and the a- mode (1100 cm1). That is, the electrode produces an unex-
Si:H structure dominated by Si-H bond configuration is shown pected oxidation side-reaction during hydrogenation, which is
in Fig. 1b. After hydrogenation, the surface of electrode sam- consistent with the results of XRD (Fig. 1e) and EDX mapping
ples became rougher and partially oxidized, and the electrode (Fig. S2d in the Supporting Information). Furthermore, to

Fig. 1 e (a) Schematic illustration of the preparation process for a-Si:H thin film electrodes and (b) a-Si:H structure dominated
by Si-H bond configuration [69]. (c) XRD patterns, (d) Raman spectra, (e) Enlarged XRD patterns, (f) FTIR spectra, and (g) High-
resolution XPS spectra of a-Si:H electrodes hydrogenated at 200, 300 and 500  C.
20242 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2

obtain more precise bond configuration information, we fitted decomposition voltage of the aqueous electrolyte (Fig. 2a). The
the XPS spectra of the electrodes (Fig. S3 in the Supporting viscosity of [EMIM][Ac] in this work is much higher than that
Information) and found that the dominant bond configurations in literature [70], so a higher concentration of glacial acetic
on the electrode surface are Si-Si, Si-H and Si-O bonds (Fig. 1g). acid is chosen to improve the conductivity of the electrolyte
It should be noted that the spectral peaks at 99.1 and 102.8 eV (Table S1 in the Supporting Information). Sintered Ni(OH)2
bond energies are dominated by SiH1.0 and SiO1.0, and the electrode was selected as the counter electrode. According to
peaks at higher H/Si and O/Si ratios typically correspond to the CV test results, the process of hydrogenation improves the
higher bond energies [88e91]. The calculated surface oxygen redox activity of the electrodes, and the higher the hydroge-
concentrations of the electrodes obtained by hydrogenation at nation temperature, the better the redox activity of the elec-
these three temperatures are all about 25%. Therefore, the trodes (Fig. 2b). The hydrogenation also reduces the electrode
hydrogen in the electrodes is predominantly configured with polarization and significantly increases the electrochemical
Si-H bond configurations accompanied by a small number of discharge capacity of the electrodes (Fig. 2c). The a-Si:H thin-
Si-H2 bond configurations, and a partial Si-O bond configura- film electrode hydrogenated at 500  C has a discharge capac-
tion at the electrode surface. ity of 1816 mAh g-1, which is about nine times that of non-
hydrogenated electrode (221 mAh g-1). The discharge capac-
Electrochemical tests ity of electrodes hydrogenated at 300  C and 200  C is 1707 and
1683 mAh g-1, respectively. Obviously, the higher hydrogena-
In the electrochemical test, the electrolyte is an anhydrous tion temperature gives the electrode a higher discharge ca-
ionic liquid electrolyte of [EMIM][Ac] mixed with 4 M glacial pacity and can greatly shortens the activation time of the
acetic acid (4 M CH3COOH/[EMIM][Ac]) and its electrochemical electrode (Fig. 2d). The activation times of the electrodes hy-
window is by 1.65 eV which is obviously higher than the drogenated at 500  C and 300  C are 33 and 32 cycles

Fig. 2 e (a) Electrochemical stability window of 4 M CH3COOH/[EMIM][Ac] electrolyte. (b) CV profiles, (c) galvanostatic charge-
discharge profiles at the optimal discharge state and (d) galvanostatic discharge profiles at the representative cycle and (e)
cycling performance and Coulombic efficiency of a-Si:H thin film electrode hydrogenated at 200, 300 and 500  C. In
Figure bec the performance of a-Si thin film electrode is used for comparison.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2 20243

Fig. 3 e (a) Energy evolution of a-Si:H electrode during MD at room temperature (RT), 200, 300 and 500  C. Electronic band
structure of the final structure evolved by MD at (b) RT, (c) 200  C, (d) 300  C and (e) 500  C for a-Si:H electrode. The data of
electrode at room temperature is used for comparison.

respectively, significantly better than the 41 cycles of the shown in Fig. 1b was constructed to investigate the effect of
electrode hydrogenated at 200  C. As can be seen from Fig. 2e, hydrogenation temperature on the electronic properties of a-
these a-Si:H thin-film electrodes have excellent cyclic stability Si:H electrodes. Since the concept of a-Si:H was proposed, its
and high coulombic efficiency. After 100 cycles, the coulombic structure has been difficult to completely determine [95,96].
efficiency of all electrodes can be maintained at about 75%, Although this structural model is not sufficient to fully reflect
and the electrodes hydrogenated at 200, 300 and 500  C still the true structure of the electrodes, it is still an effective way to
have an electrochemical discharge capacity of 1080, 1127 and understand the electronic properties of a-Si:H electrodes by
960 mAh g-1, respectively. These results are significantly bet- calculating the electronic properties of supercell with more
ter than the performance of the electrodes in our previous atoms. The supercell was simulated with MD in canonical
work [71], which is mainly due to the use of thinner film ensemble (NVT) at room temperature (RT), 200, 300 and 500  C,
electrodes in this work and the thinner electrodes tend to respectively, to obtain the most stable structure at these tem-
correspond to better electrochemical cycle stability, as re- peratures. As can be seen from the energy evolution with the
ported in lithium-ion battery [92e94]. ion step size of the MD simulation in Fig. 3a, the total energies
As can be seen from the experimental results, the hydro- of these structures do not decrease but increases after 10000 fs,
genation process significantly improves the electrochemical which is most likely due to the high convergence accuracy
properties of the a-Si electrodes, however, in order to more adopted in the optimization of these structures prior to MD
accurately reveal the intrinsic reasons for the enhancement of simulations. Calculations of the electronic properties of these
the electrochemical properties, it is necessary to further final structures evolved by MD (Fig. S4 in the Supporting In-
investigate and analyze the electrochemical hydrogen storage formation) indicate that the conduction band of the a-Si:H
behavior of the a-Si:H electrodes during charge/discharge electrode is shifted downward and the band gap decreases
processes, such as the electronic properties of the electrodes with increasing hydrogenation temperature (Fig. 3bee).
in different electrochemical states, the hydrogen diffusion Generally, a small band gap can reduce the electrode polari-
mechanism from the electrode surface to the bulk, the zation and increase the discharge capacity of the electrode,
competing mechanisms of hydrogen storage and HER at the which is in agreement with the experimental results and may
electrode surface, and the electronic properties of electrode/ well explain the internal causes of the minimum electrode
substrate interface. polarization and the maximum electrochemical capacity ob-
tained by electrode hydrogenation at 500  C.
3.3. Electronic properties of a-Si:H electrodes Furthermore, for semiconducting electrodes, both Faradaic
and non-faradaic processes should present simultaneously
The electronic properties of the electrodes have important ef- when the electrode reactions occur [97]. When the charging
fects on their electrochemical behavior, such as the electrode current is small, or during the initial charging, the potential
polarization and the thickness of the electrical double-layer. difference near the electrode/electrolyte interface is not large
These effects may require more attention for electrodes with enough for the electrons to complete the transition from the
semiconducting properties than for metal alloy electrodes with valence to conduction band, leading to no electrons reached
good electrical conductivity. A supercell of the a-Si:H structure the electrode/electrolyte interface, that is, no charge transfer
20244 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2

reaction takes place at this interface, the proton adsorbed at as the hydrogen content of the electrode continues to in-
the electrode/electrolyte interface can only serve the purpose crease, its electronic structure becomes extremely unstable,
of electrochemical hydrogen storage by first physical adsorp- alternating between semiconductor and conductor, but the
tion followed by chemical absorption (non-faradaic pro- band gap of the electrode structure tends to decrease when
cesses). As the charging current or the charge time increases, the electrode exhibit semiconductor properties in the later
some electrons reach the electrode/electrolyte interface via charging process. While the electrode behaves like a
the transition and cross the inner Heimholtz plane (IHP) into conductor, the probability of Faradaic processes in the elec-
the outer Heimholtz plane (OHP) to participate in the redox trode reaction increases significantly, which increases the
reaction with glacial acetic acid (Faradaic processes). It is clear proton concentration at the electrode/electrolyte interface
that a smaller band gap electrode will bring the location of the and the proton concentration gradient from the interface to
electron accumulation closer to the electrode/electrolyte the bulk of electrode, thus increasing the proton diffusion
interface, that is, reduce the thickness of electrical double rate. Therefore, during the first half of the charging process,
layer, which greatly increases the probability of electrons that is, as the charge capacity is less than 1046 mAh g1
entering OHP and participating in the electrode reaction and (corresponds to 3.44 wt% hydrogen content), a-Si:H electrode
proton production. Therefore, increasing the hydrogenation has a fast charge rate, but during the second half of the
temperature is beneficial for improving the electrochemical charging process (charge capacity reaches and exceeds 1046
properties of the a-Si:H electrodes. mAh g1), the charging rate of the electrode fluctuates some-
To further reveal the variety rule of electronic properties of what due to the instability of the electronic structure of elec-
a-Si:H electrode during electrochemical charge-discharge trode, which is basically consistent with the experimental
process, the structure in Fig. 1b was used as a sample to results (Fig. S6 in the Supporting Information).
adjust the hydrogen content in the structure to obtain the In addition, since the surface of the a-Si:H electrode pre-
structure of a-Si:H electrodes at different stages of the elec- pared in this work is covered by approximately 25% oxygen,
trochemical charge-discharge process (Fig. S5 in the Sup- it is necessary to investigate the effect of oxygen on the
porting Information). The partial density of states (PDOS) of electrode properties of the electrode. The slab models of a-
these a-Si:H electrode structures with different hydrogen Si:H electrodes with different oxygen surface coverage are
content are presented in Fig. 4. It can be seen that the elec- presented in Fig. 5a and their corresponding partial density
trode without hydrogen storage or with deep discharge is a of states are shown in Fig. 5bef. It can be found that the
semiconductor structure with a band gap of about 0.65 eV. As conductivity of the electrode surface is relatively good at low
the charging process proceeds, the hydrogen content of the oxygen coverage and decreases with increasing oxygen
electrode increases and the electrode first becomes a coverage. That is, the oxygen atoms adsorbed on the elec-
conductor and then the conductivity gradually decreases. trode surface do not prevent the free passage of electrons
When the hydrogen content of the electrode reaches 3.44 wt%, through the electrode/electrolyte interface for electrode
the electrode again becomes a semiconductor structure, and reaction.

Fig. 4 e Partial density of states (PDOS) of a-Si:H electrode at each stable stage during charge/discharge.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2 20245

Fig. 5 e (a) Structural schematic diagram and the corresponding partial density of states (PDOS) for a-Si:H electrode with
oxygen surface coverage of (b) 0%, (c) 25%, (d) 50%, (e) 75% and (f) 100%.

Following the electronic properties, the ability of the elec- early and late charging stages, but easy in the intermediate
trode to adsorb hydrogen at various stages of the charge- charging stages, which may be one of the reasons for the low
discharge process is also indispensable for the electrode per- discharge capacity of the non-hydrogenated electrodes but
formance. As can be seen from Fig. 6a, when the charging the high discharge capacity of the hydrogenated electrodes.
capacity of the electrode is lower or higher, it needs to absorb As the charging process proceeds, the increase of the
some external energy such as the electric field energy to hydrogen content in the electrode leads to the expansion of
accomplish the hydrogen adsorption, but once the electro- the electrode volume. When the charging capacity reaches a
chemical hydrogen storage capacity of electrode is between maximum of 1816 mAh g1 (corresponds to 6.0 wt% hydrogen
532 and 1667 mAh g1 (corresponding hydrogen content range content), the electrode volume is approximately twice that of
is 1.75e5.48 wt%), the hydrogen adsorption process is spon- the non-hydrogenated electrode. In contrast, the electrode
taneous. That is, the charging process is relatively hard in the volume tends to decrease during the discharge. The

Fig. 6 e (a) Hydrogen adsorption energy and volume change of a-Si:H electrode at each stable stage during charge/discharge
and (b) hydrogen adsorption and oxygen desorption energies of a-Si:H electrode at different oxygen surface coverage.
20246 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2

Fig. 7 e (a) Schematic diagram of hydrogen diffusion pathways from surface to subsurface and then to bulk for a-Si:H and a-
Si electrodes. Energy profiles of hydrogen diffusing (b) from surface to subsurface and (c) from subsurface to bulk for a-Si:H
and a-Si electrodes.

expansion and contraction of the electrode during charge and to be absorbed, or the energy barrier to be surpassed, for the
discharge should result in some degree of irreversible struc- diffusion of hydrogen from the surface to the subsurface and
tural change of the electrode, which may impair the electro- then to the bulk. The hydrogen diffusion pathway is presented
chemical cycle stability of the electrodes to some extent. As in Fig. 7a and the corresponding calculated energy barrier is
the electrode thickness increases, the amplitude of the shown in Fig. 7bec, where the energy barrier for a-Si electrode
expansion/contraction during charging/discharging in- is used for comparison. It can be found that both from surface
creases, which greatly increases the probability of chap or to subsurface and from subsurface to bulk, the corresponding
even pulverization of the electrode, resulting in a very low diffusion energy barriers for a-Si:H electrode are all smaller
cycle life. This may be one of the main reasons why the than those for a-Si electrode, that is, the diffusion of hydrogen
electrochemical cycle stability of thinner electrodes is signif- from the surface to the bulk, or the electrochemical hydrogen
icantly better than that of thicker ones. Moreover, Fig. 6b storage process, is easier to accomplish for the a-Si:H elec-
shows that both the ability of the electrode to absorb hydrogen trodes than for the a-Si electrodes. Additionally, the inverse
and the energy required for oxygen desorption from the sur- process of hydrogen diffusion from the surface to the bulk can
face gradually decrease as the oxygen coverage increases. be used to assess the capability of the electrochemical
That is, the adsorption of a small number of oxygen atoms at hydrogen release. It is obvious that both from bulk to sub-
the electrode surface does not prevent the electrode from surface and from subsurface to surface, the hydrogen diffu-
absorbing and storing hydrogen, but the high oxygen coverage sion energy barrier is also smaller for a-Si:H electrode
increases the difficulty of hydrogen adsorption onto the compared to a-Si electrode, suggesting that the electro-
electrode surface. The fact that the oxygen desorption energy chemical hydrogen release is faster for a-Si:H electrode than
decreases with increasing oxygen coverage at the electrode for a-Si electrode. As a result, the a-Si:H electrodes have better
surface may lead to a dynamical equilibration of oxygen electrochemical hydrogen storage/release reversibility
desorption and oxygen adsorption at a certain oxygen compared to the a-Si electrode, which may be one of the chief
coverage during hydrogenation, which may be the reason for causes of the apparent improvement in the electrochemical
the 25% oxygen coverage of the electrodes hydrogenated at properties of the electrode after hydrogenation.
different temperatures. The hydrogen diffusion mechanism in the bulk of a-Si:H
electrodes was predicted by comparing the energy barriers for
Hydrogen diffusion mechanism hydrogen diffusion through different types of bonds and
different diffusion pathways. The hydrogen diffusion path-
The capability of hydrogen to diffuse from the electrode sur- ways are shown in Fig. 8a and their corresponding diffusion
face to the bulk is particularly important for hydrogen storage energy barriers are presented in Fig. 8b. The energy barrier for
electrodes, especially for non-faraday processes in electrode hydrogen diffusion through an empty hanging bond is 0.39 eV,
reactions. This capability is evaluated by the energy required which is about 0.56 eV smaller than that for hydrogen diffusion
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2 20247

Fig. 8 e (a) Schematic diagram of hydrogen diffusion pathways and (b) the corresponding energy profiles of hydrogen
diffusing in the bulk of a-Si:H electrode.

through a hydrogen bond. This implies that the diffusion of time, the glacial acetic acid (CH3COOH) in the electrolyte is
hydrogen through the empty dangling bonds should be quicker physically adsorbed onto the OHP of electrical double layer.
as the concentration of hydrogen in the electrode is lower in Under the influence of the electric field energy, some electrons
the early stages of the electrochemical charge process or in the pass through the electrode/electrolyte interface and enter the
late stages of the electrochemical discharge process, in OHP where they react with the glacial acetic acid and
contrast to the smaller hydrogen diffusion rate through the decompose it into an acetic acid root (CH3COO) and a proton
hydrogen bonds in the late charging and early discharging (Hþ), and then proton enters the IHP and is captured by the
processes. By comparing the diffusion energy barriers of electrode and chemically absorbed. This process is better
hydrogen diffusing directly from position 1 to position 3 (path known as the electrochemical adsorption. Electrochemical
1) with that of hydrogen of position 1 diffusing to position 2 desorption refers to the reaction of a new electron with a new
while hydrogen of position 2 diffusing to position 3 at the same glacial acetic acid, resulting in a new acetic acid root and a
time (path 2, hopping mechanism), it can be seen that the new proton, the acetic acid root moves away from the OHP
diffusion energy barrier of the latter is less than half that of the and enters the electrolyte across the diffuse layer under the
former, indicating that the long-distance diffusion of hydrogen repulsive force of the electric field, while the new proton en-
in the a-Si:H electrodes with high hydrogen content is likely to ters the IHP and combines with the hydrogen chemisorbed on
be accomplished by a hopping mechanism, in general agree- the electrode surface (H*) to form hydrogen gas (H2). Un-
ment with the conjecture in our previous work [71]. In addition, doubtedly, for proton batteries, electrochemical adsorption is
the effect of oxygen on hydrogen diffusion near the electrode a necessary and beneficial process for the proton production
surface is investigated (Fig. S7 in the Supporting Information). by electrode reactions, but electrochemical desorption to
It has been shown that the oxygen coverage on the electrode produce irreversible H2 is a side-reaction that should be
surface significantly increases the energy barrier for hydrogen avoided as much as possible (Schematic diagram of HER is
diffusion both from the surface to the subsurface and from the shown in Fig. S8 in the Supporting Information).
subsurface to the surface compared to the hydrogen-modified Fig. 9 shows the Gibbs free energy at each stage of the HER
electrode surface, so that the oxygen coverage of the electrode process for a-Si:H electrode in CH3COOH/[EMIM][AC] electro-
surface is clearly detrimental to the hydrogen absorption/ lyte. The Gibbs free energy of chemisorption of hydrogen
desorption near the electrode surface and thus severely affects atoms on the electrode surface is defined by the equation
the reversibility of electrochemical hydrogen storage/release [100,101].
in a-Si:H electrodes.
DGH* ¼ DEH þ DEZPE  TDSH (1)
Electrochemical hydrogen evolution reaction
1
DEH ¼ EH=electrode  Eelectrode  EH2 (2)
2
For a new battery system, it is necessary to investigate elec-
trochemical HER for the electrodes at their interface with the
1 H2
electrolyte. Electrochemical HER proceeds include electro- DEZPE ¼ EH*
ZPE  EZPE  EZPE (3)
2
chemical adsorption (Volmer reaction) and electrochemical
desorption (Heyrovsky reaction) [98,99]. For this novel proton where DEH is the differential hydrogen adsorption energy, T,
battery, during charging, electrons accumulate on the elec- temperature, DEZPE , the difference energy in zero-point en-
trode side near the electrode/electrolyte interface, at the same ergy, DSH , the entropy between hydrogen adsorption on the
20248 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2

Fig. 9 e Relative energy profiles of the various species along the HER pathway for a-Si:H electrode. The energy profiles of
hydrogen diffusing from electrode surface to bulk are used for comparison. In the figure IR refers to the initial state of HER,
TS to the transition state of HER and ER to the end of HER.

electrode surface and in the gas phase [102], EH=electrode and hydrogen diffuse from surface to bulk, indicating that elec-
Eelectrode are the total energies of the electrode slab model with trochemical hydrogen storage is easier compared to electro-
and without hydrogen adsorbed on its surface, EH2 is the total chemical desorption, and that the side-reaction of
energy of H2 in the gas phase, EH*
ZPE and EZPE are the zero-point
electrochemical desorption occurs only if the electric field
energy of electrode slab model with and without hydrogen energy at the electrode surface is too high or if the electrode
adsorbed on its surface, respectively. EH polarization is relatively serious, which is clearly very favor-
ZPE is the zero-point
2

energy of H2 in the gas phase. It can be found that the phys- able for electrochemical hydrogen storage for the a-Si:H
ical adsorption of glacial acetic acid on the electrode surface is electrodes.
spontaneous, which provides the enabling conditions for the
subsequent HER process. The decomposition of glacial acetic Electronic properties of electrode/substrate interface
acid at the electrode surface requires an absorption energy of
about 2.3 eV and the subsequent adsorption of protons at the In order to have a more complete understanding of the
electrode surface is a spontaneous process. To predict the physical properties of the a-Si:H electrode during electro-
competing mechanisms between hydrogen storage in the chemical processes, in addition to the above analysis of elec-
electrodes and electrochemical desorption, the energy bar- tronic properties and electrochemical behavior of the
riers that hydrogen needs to surpassed to diffuse from the electrode, the physical properties of the electrode/substrate
surface to the bulk are used for comparison. It is not difficult to interface are also predicted. Inspired by the easier growth of
find that the energy required for electrochemical desorption at silicon and amorphous silicon films on Ag(111) surface
the electrode surface is about 2.56 eV larger than that for [103,104] and the fact that nickel and silver have the same

Fig. 10 e (a) Side view of difference charge density and (b) partial density of states (PDOS) for the most stable interface
configuration of a-Si:H thin film electrode on Ni(111) substrate and Ni(200) substrate, (c) Diffusion energy profiles of an
individual silicon atom on Ni(111) surface and Ni(200) surface. In Figure a, blue and yellow regions indicate electron
depletion and accumulation, respectively. (For interpretation of the references to colour in this figure legend, the reader is
referred to the Web version of this article.)
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 0 2 3 8 e2 0 2 5 2 20249

face-centered cubic structure, the Ni(111) surface and a-Si:H electrodes applied to other types of batteries during charge/
structure are chosen to construct the slab model to simulate discharge processes.
electrode/substrate interfaces, and the slab model of elec-
trode/substrate interface based on the Ni(200) surface is used
for comparison. The difference charge density and the partial Declaration of competing interest
density of states of these slab models are presented in
Fig. 10aeb. It can be found that the electrons near the elec- The authors declare that they have no known competing
trode/substrate interface are redistributed and the electrode/ financial interests or personal relationships that could have
substrate interfaces both for Ni(111) and Ni(200) surfaces appeared to influence the work reported in this paper.
exhibit conductive properties, indicating that electrons can
easily pass through these two interfaces without affecting the
electrochemical charging and discharging of the electrodes.
Acknowledgments
As can be seen from Fig. 10c, the silicon atom has a very small
diffusion energy barrier on the Ni(111) surface, about 0.067eV,
This work is financially supported by national natural science
which indicates that a-Si thin film can grow rapidly on the
foundation of china (22065020).
Ni(111) surface during deposition. The diffusion energy barrier
of silicon atoms on the Ni(200) surface is about 15 times that
on the Ni(111) surface. The high diffusion energy barrier
Appendix A. Supplementary data
usually corresponds to the poor thermal stability [105], that is
to say, compared with the Ni(111) surface, the thin film elec-
Supplementary data to this article can be found online at
trode grown on the Ni(200) surface is more prone to stripping
https://doi.org/10.1016/j.ijhydene.2023.03.034.
during the process of hydrogenation and electrochemical
charge-discharge, which can be used to analyze the source of
the decrease of the electrochemical capacity as the number of references
electrochemical cycles increases.

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