RESEARCH ARTICLE
All-Solid-State Magnesium Batteries
Borohydride Ammoniate Solid Electrolyte Design for
All-Solid-State Mg Batteries
Yuepeng Pang, Zhengfang Nie, Fen Xu, Lixian Sun , Junhe Yang, Dalin Sun, Fang Fang*,
and Shiyou Zheng*
Searching for novel solid electrolytes is of great importance and challenge for
all-solid-state Mg batteries. In this work, we develop an amorphous Mg
borohydride ammoniate, Mg(BH4)2
2NH3, as a solid Mg electrolyte that
prepared by a NH3 redistribution between 3D framework-c-Mg(BH4)2 and
Mg(BH4)2
6NH3. Amorphous Mg(BH4)2
2NH3 exhibits a high Mg-ion
conductivity of 5 3 10 4 S cm 1 at 75 °C, which is attributed to the fast
migration of abundant Mg vacancies according to the theoretical
calculations. Moreover, amorphous Mg(BH4)2
2NH3 shows an apparent
electrochemical stability window of 0–1.4 V with the help of in-situ formed
interphases, which can prevent further side reactions without hindering the
Mg-ion transfer. Based on the above superiorities, amorphous Mg(BH4)2
2NH3
enables the stable cycling of all-solid-state Mg cells, as the critical current
density reaches 3.2 mA cm 2 for Mg symmetrical cells and the reversible
specific capacity reaches 141 mAh g 1 with a coulombic efficiency of 91.7%
(first cycle) for Mg||TiS2 cells.
1. Introduction
Rechargeable Mg batteries have been considered as promising energy
storage devices due to its high theoretical energy densities and abun-
dant earth reserves.[1] Mg possesses two charges per ion, indicating that
1/12 mol electron can be transferred by 1 g Mg, which is close to that
of Li (1/7 mol electron by 1 g Li). In addition, the negative redox
potential of Mg is 2.36 V (vs SHE), also close to that of Li
( 3.05 V).[2,3] More importantly, the reserves of Mg in earth’s crust is
2.3 wt%, much higher than that of Li (0.0065 wt%).[4]
Electrolytes are the key component in rechargeable Mg batteries,
since their Mg-ion conductivity, the electrochemical stability window
and the electrode compatibility of the electrolytes all significantly affect
Dr. Y. Pang, Z. Nie, Prof. J. Yang, Prof. S. Zheng
School of Materials and Chemistry, University of Shanghai for Science and
Technology, Shanghai 200093, China
E-mail: syzheng@usst.edu.cn
Prof. F. Xu, Prof. L. Sun
Guangxi Key Laboratory of Information Materials & Guangxi Collaborative
Innovation Centre of Structure and Property for New Energy and Materials,
Guilin University of Electronic Technology, Guilin 541004, China
Prof. D. Sun, Prof. F. Fang
Department of Materials Science, Fudan University, Shanghai 200433, China
E-mail: f_fang@fudan.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/eem2.12527.
DOI: 10.1002/eem2.12527
Energy Environ. Mater. 2022, 0, e12527 1 of 7
the overall performance of the rechargeable Mg
batteries.[5] Different from rechargeable Li bat-
teries, the interphase in the Mg anode side is
non-ion-conductive when using carbonate-
based electrolytes.[6] Meanwhile, ether-based
electrolytes, such as Grignard reagents (or
derivations)[7] and simple Mg salt (MgCl2, Mg
(CB11H12)2)[8,9] solutions can enable reversible
Mg stripping and plating, however, at least one
of the following key issues still exists for these
electrolytes: incompatibility to electrode, corro-
sivity against stainless steel, and difficulty for
synthesis.[10,11]
The application of solid Mg electrolytes can
potentially avoid the drawbacks of liquid Mg
electrolytes by providing an intrinsically differ-
ent ion conducting mechanism. For example,
1) solid Mg electrolytes are much safer due to
their nonvolatility, noninflammability and non-
corrosivity; 2) solid Mg electrolytes can sup-
press the dendritic Mg growth during fast plating; 3) solid Mg
electrolytes can simplify the large-scale battery packaging.[12,13] On the
other hand, the solid-state diffusion of high-valence Mg ions is usually
difficulty due to the strong bonds with counter anions.[14] Therefore,
investigations on solid Mg electrolytes are mainly focused on the
improvement in Mg-ion conductivity.[15] Many classes of materials,
such as oxides (MgZr4(PO4)6[16]), sulfides (MgS–P2S5–MgI2[17]), and
selenides (MgSc2Se4[18]), have been investigated as solid Mg electrolytes
and significant improvements have been achieved. Since Higashi
et al.[19] reported that Mg(BH4)(NH2) can exhibit a high Mg-ion con-
ductivity (10 6 S cm 1 at 150 °C) at 2014, complex hydrides with
unique B–H and N–H bonds become the most promising candidates
as solid Mg electrolyte materials.[20–22] Le Ruyet et al.[23] proposed
that Mg3(BH4)4(NH2)2 exhibits higher Mg-ion conductivity of
4.1 9 10 5 S cm 1 at 100 °C. Roedern et al.[24] found that Mg
(BH4)2(NH2CH2CH2NH2) possesses higher Mg-ion conductivity of
5 9 10 8 S cm 1 at 30 °C. Kisu et al.[25] developed Mg
(BH4)2
(NH3BH3)2 as solid Mg electrolyte, which exhibits a Mg-ion
conductivity of 10 5 S cm 1 at 30 °C. More recently, Yan et al.[26]
investigated Mg borohydride ammoniates as solid Mg electrolytes, in
which Mg(BH4)
NH3 was reported to show a Mg-ion conductivity of
2 9 10 9 S cm 1 at 30 °C. Moreover, they found that dramatical
improvement in conductivities (more than four orders of magnitude)
can be achieved by the interaction between Mg borohydride ammoni-
ates and oxygen vacancies in metal oxides.[27–29]
However, further exploration is still highly needed for pushing
the complex hydride electrolytes toward practical applications in
© 2022 The Authors. Energy & Environmental Materials published by
John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.
This is an open access article under the terms of the Creative Commons
Attribution License, which permits use, distribution and reproduction
in any medium, provided the original work is properly cited.

all-solid-state Mg batteries. First, the Mg-ion conduction mechanism
has not been clearly identified, especially in terms of Mg vacancy
migration mechanism, which hinders the future improvement in Mg-
ion conductivity. Second, the corresponding physical and chemical
interactions on the electrode/electrolyte interfaces in all-solid-state bat-
teries have not been clarified, which generates a huge gap between the
Mg-ion conduction properties of the electrolytes and the electrochemi-
cal performances of the all-solid-state batteries.[30,31]
In this work, an amorphous Mg borohydride ammoniate, Mg
(BH4)2
2NH3, is prepared through a NH3 redistribution between 3D
framework c-Mg(BH4)2 and Mg(BH4)2
6NH3. Amorphous Mg
(BH4)2
2NH3 shows excellent Mg-ion conduction properties, as a Mg-
ion conductivity of 1 9 10 7 S cm 1 at 35 °C and 5 9 10 4 S cm 1
at 75 °C can be obtained. Density functional theory calculations reveal
that the Mg vacancy migration play an important role in the Mg-ion
conduction, and Mg(BH4)2
2NH3 has lower energy barriers than those
of c-Mg(BH4)2 and Mg(BH4)2
NH3. The apparent electrochemical sta-
bility window of amorphous Mg(BH4)2
2NH3 reaches 0–1.4 V
Figure 1. a) Schematic illustration of the design principle of am-Mg(BH4)2
2NH3. b) X-ray diffraction
patterns, c) Raman spectra, d) transmission electron microscope image (inset: selected area electron exothermic signals reflect the dehydrogena-
diffraction pattern), and e) differential scanning calorimetry curves of c-Mg(BH4)2, Mg(BH4)2
6NH3, tion.
and am-Mg(BH4)2
xNH3 (x = 1, 2, 3).
Energy Environ. Mater. 2022, 0, e12527
25750356, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12527 by Birla Institute of Technology & Science - Pilani, Wiley Online Library on [29/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
accompanying with interphases formation. Moreover, the excellent con-
ductivity and stability of amorphous Mg(BH4)2
2NH3 enables cycling
of all-solid-state Mg symmetrical cells and Mg|TiS2 cells.
2. Results and Discussion
Figure 1a schematically illustrates the material design principle, in
which NH3 redistribution occurs between unique 3D microporous
structured c-Mg(BH4)2 and Mg(BH4)2
6NH3 to form amorphous Mg
(BH4)2
2NH3 during high-energy ball milling, benefitting the fast Mg-
ion transfer. Then, the structural characterizations of the as-prepared Mg
(BH4)2
xNH3 (x = 1, 2, 3), c-Mg(BH4)2, and Mg(BH4)2
6NH3 are per-
formed. X-ray diffraction patterns (Figure 1b) show that c-Mg(BH4)2
and Mg(BH4)2
6NH3 exhibit typical diffraction peaks without any
impurity signal. As for Mg(BH4)2
xNH3 (x = 1, 2, 3), no apparent
diffraction peak can be observed, indicating they are mainly amorphous.
Some minor peaks in these samples correspond to the small amount of
a-Mg(BH4)2 impurity in c-Mg(BH4)2. Raman
measurements (Figure 1c) demonstrate that
apparent N–H vibration signals can be found at
3178, 3270, and 3346 cm 1 for Mg
(BH4)2
xNH3, implying that all N atoms are in
the NH3 group. In addition, B–H bonds can be
detected in the wavenumber range of 2000–
2600 cm 1 for all samples. The B–H vibration
signal is different for each sample and their char-
acteristic peaks fit well with the previous works,
indicating a successful preparation of single
phase Mg(BH4)2
xNH3 (x = 1, 2, 3).[32,33]
Figure 1d presents the transmission electron
microscope (TEM) results of a representative
Mg(BH4)2
2NH3 sample, in which irregular
particles with a diameter of 200 nm can be
observed in the image and broad and vague
rings can be detected in the selected area elec-
tron diffraction pattern, further confirming that
the as prepared Mg(BH4)2
2NH3 is composed
of amorphous submicron particles. It should be
noted that low dose and short time electron
beam irradiation should be used to avoid the
melting of Mg(BH4)2
2NH3.
The thermal stability of Mg(BH4)2
xNH3
(x = 1, 2, 3) and reference samples are evalu-
ated using differential scanning calorimetry
(DSC, Figure 1e). Endothermic peaks at above
182 °C can be found for c-Mg(BH4)2, corre-
sponding to the c to b phase transformation
and dehydrogenation.[34] For Mg(BH4)2
6NH3,
complex heat flows are detected at above
172 °C, corresponding to the successive NH3
and H2 desorption.[35] The endothermic peaks
at 92 °C and 100 °C (starts at above 85 °C,
Figure S1, Supporting Information) are the
melting of Mg(BH4)2
NH3 and Mg
(BH 4)2
2NH3, respectively, and the following
[26]
Moreover, Mg(BH4)2
3NH3 succes-
sively releases NH3, melts and desorbs H2 in
2 of 7 © 2022 The Authors. Energy & Environmental Materials published by
John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.

the temperature range of 120–250 °C.[35] The apparent differences in
melting temperature and enthalpy change further confirm the occur-
rence of NH3 redistribution reaction.
The above results reveal that amorphous Mg(BH4)2
xNH3 (x = 1, 2,
3), that is am-Mg(BH4)2
xNH3, can be successfully prepared by high-
energy ball milling c-Mg(BH4)2 and Mg(BH4)2
6NH3 with certain
ratios and they can maintain physically and chemically stable at below
85 °C. It should be noted here that this amorphization is closely related
to the unique microporous structure of c-Mg(BH4)2,[36] which is liable
to adsorb molecules and collapse into amorphous phase in only several
hours (Figure S2, Supporting Information), and Mg(BH4)2
xNH3 pre-
pared via a same procedure using b-Mg(BH4)2 is crystalline, not amor-
phous (Figure S3, Supporting Information).
The Mg-ion conduction properties of am-Mg(BH4)2
xNH3 (x = 1,
2, 3) and reference samples are measured in terms of conductivities
and transference numbers. The conductivity of the electrolyte is calcu-
lated from the electrochemical impedance spectroscopy (EIS) of block-
ing cells (Figure S4, Supporting Information). Figure 2a shows the
temperature-dependent conductivities of am-Mg(BH4)2
xNH3 (x = 1,
2, 3), in which am-Mg(BH4)2
xNH3 (x = 1, 2, 3) all exhibit much
higher conductivities in the temperature range of 35–85 °C than those
of c-Mg(BH4)2 and Mg(BH4)2
6NH3. Among them, am-Mg
(BH4)2
2NH3 shows the highest conductivity, as 1 9 10 7 S cm 1 at
35 °C and 5 9 10 4 S cm 1 at 75 °C can be achieved, which are
already acceptable for all-solid-state Mg battery cycling. It is noteworthy (Evf) for Mg(BH4)2
2NH3 is calculated to be 1.92 eV, which is lower than
that the conductivity of am-Mg(BH4)2
NH3 is only slightly lower than
that of am-Mg(BH4)2
2NH3, so the following investigations are mainly
focused on these two samples. The activation energies of Mg-ion
migration (Ea) for am-Mg(BH4)2
2NH3 and am-Mg(BH4)2
NH3 are
calculated to be 1.99 and 2.15 eV, respectively (Figure S5, Supporting
Information).
Figure 2. a) Temperature-dependent conductivities of c-Mg(BH4)2, Mg(BH4)2
6NH3 and am-Mg ment under different temperatures and mea-
(BH4)2
xNH3 (x = 1, 2, 3). b, c) Transference number measurements of am-Mg(BH4)2
2NH3 by direct sure their Mg-ion conduction properties
current polarization and electrochemical impedance spectroscopy at 75 °C.
Energy Environ. Mater. 2022, 0, e12527 3 of 7
25750356, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12527 by Birla Institute of Technology & Science - Pilani, Wiley Online Library on [29/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Direct current (DC) polarization and EIS tests are then performed on
blocking cells and Mg symmetric cells at 75 °C to show the transfer-
ence numbers of am-Mg(BH4)2
xNH3 (x = 1, 2). Figure 2b presents
that the electronic conductivity is 3 9 10 9 S cm 1 for am-Mg
(BH4)2
2NH3, corresponding to an electronic transference number of
close to 0. In addition, the Mg-ion transference number is calculated to
be 0.95 according to the currents and resistances (Figure 2c) at the ini-
tial and steady polarization states of Mg symmetric cells, suggesting that
it is a single Mg-ion conductor. As for am-Mg(BH4)2
NH3, the transfer-
ence numbers are similar (Figure S6, Supporting Information).
Based on the above results, we know that am-Mg(BH4)2
2NH3 exhi-
bits much improved conductivities with high Mg-ion transference
numbers, which is a very promising solid electrolyte candidate for
solid-state Mg batteries.
To elucidate the mechanism of fast Mg-ion conduction in am-Mg
(BH4)2
2NH3, density functional theory (DFT) calculations are carried
out with c-Mg(BH4)2 and am-Mg(BH4)2
NH3 as reference samples.
Crystal Mg(BH4)2
2NH3 exhibits a space group of orthorhombic
Pcab with unit cell parameters of a = 17.482
A, b = 9.4132
A,
c = 8.7304
A and Z = 8, which is built by layered packing of pseudo
tetrahedral Mg(BH4)2
2NH3 molecules.[37]
It is known that Mg-ion conduction can be achieved by vacancy migra-
tion and/or interstitial migration. We therefore paid special attention to
the calculations on the point defects. The Mg vacancy formation energy
the Mg interstitial formation energy (2.21 eV). We thus believe that the
Mg vacancy migration is the main contributor to the Mg-ion conduction
in Mg(BH4)2
2NH3. Similar results can also be obtained for c-Mg(BH4)2
and Mg(BH4)2
NH3 (Table S1, Supporting Information).
As shown in Figure 3a–c, the optimized Mg vacancy migration
paths to equivalent sites along different axes involve zigzag routes
through intermediate sites. For the migration
along a, b and c axes, 3, 1, and 1 intermediate
site is needed, and the energy barriers for migra-
tion (Evm) are 1.02, 0.96, and 0.83 eV, respec-
tively (Figure 3d). As a comparison (Figure 3e),
c-Mg(BH4)2, and Mg(BH4)2
NH3 possess
higher energy barriers for Mg vacancy migration
(respectively 1.32 and 0.91 eV, Figure S7).
It should be noted that am-Mg(BH4)2
2NH3
and am-Mg(BH4)2
NH3 are amorphous (short-
range ordered but long-range disordered) in
this work, which have similar but distinct
Mg-ion conduction behaviors to crystalline
counterparts that are investigated by DFT cal-
culations. It has been reported that the amor-
phization can generally lead to the decrease in
Evf and Evm.[38,39] Here, we confirm this by
both experiments and calculations. Theoreti-
cally, Ea equals to the sum of Evf and Evm.[40]
However, Ea of am-Mg(BH4)2
2NH3 and am-
Mg(BH4)2
NH3 (1.99 and 2.15 eV) are smal-
ler than calculated values (2.75 and 2.58 eV),
which is one evidence for the decrease in Evf
and Evm by amorphization. In addition, we
recrystallize am-Mg(BH4)2
2NH3 by heat treat-
(Figures S8 and S9, Supporting Information).
© 2022 The Authors. Energy & Environmental Materials published by
John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.

Figure 3. a–c) Schematic illustration of Mg-ion diffusion paths along a, b, and c axes of Mg identify its long-term compatibility to Mg anode
(BH4)2
2NH3. d) Mg-ion diffusion energy barriers of Mg(BH4)2
2NH3. e) Comparison of the lowest at 75 °C. As shown in Figure 5a, the Mg sym-
diffusion energy barrier between c-Mg(BH4)2, Mg(BH4)2
NH3, and Mg(BH4)2
2NH3.
The conductivity decreases and Ea increases after recrystallization,
which can further prove the effect of amorphization on Evf and
Evm. The above results show that the apparently reduced Evf and
Evm by amorphization are mainly responsible for the super Mg-ion
conduction in am-Mg(BH4)2
2NH3.
Electrochemical stability is another key parameter that determines
the overall performances of electrolytes. Figure 4a presents the cyclic
voltammetry (CV) curves of Mg|am-Mg(BH4)2
2NH3|Mo cell at
75 °C in the potential range of 0.2 to 1.4 V (vs Mg2+/Mg), in which
only symmetric current peaks (more than 90 lA) near 0 V is observed,
corresponding to the Mg plating and stripping on the Mo electrode
(Figure S10, Supporting Information). This result indicates that the
apparent electrochemical stability window reaches 0–1.4 V. In addi-
tion, the result (Figure S11, Supporting Information) for am-Mg
(BH4)2
NH3 shows that its electrochemical stability window is nar-
rower, ranging in 0–1.3 V, agreeing well with reference. [26]
To reveal the exact electrochemical behaviors of am-Mg
(BH4)2
2NH3 at limiting potentials, we repeatedly scan the Mg|am-Mg
(BH4)2
2NH3|Mo cells from open circuit voltage to 0 and 1.4 V,
respectively (Figure 4b,c). Small current signals (<4 lA) can be
Energy Environ. Mater. 2022, 0, e12527
25750356, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12527 by Birla Institute of Technology & Science - Pilani, Wiley Online Library on [29/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
observed in the first scans when the potential is
smaller than 0.6 V and larger than 0.9 V, and
the current signals reduce significantly to close
to 0 in the following scans, which suggest that
1) interphases, that is solid electrolyte interphase
(SEI) and cathodic electrolyte interphase (CEI),
are formed at the Mo/am-Mg(BH4)2
2NH3
interface and 2) the interphases stabilize the
interface by hindering further side reactions
(Figure S12, Supporting Information).[41,42]
The results for the cells with carbon additives
(Figure S13, Supporting Information) also sup-
port this conclusion.
In addition, EIS measurements (Figure 4d)
before and after scanning are performed to eval-
uate the resistances of the SEI and CEI. The fresh
Mg|am-Mg(BH4)2
2NH3|Mo cell has only a SEI
at the Mg/electrolyte interface, and its resistance
is 1338 Ω. After scanning, the newly formed
SEI and CEI at the cathode/electrolyte interface
lead to resistance increases, as the chord lengths
of the semicircles reach 2575 and 1910 Ω,
respectively, indicating that the SEI and CEI pos-
sess lower (compared with that of am-Mg
(BH4)2
2NH3) but still acceptable Mg-ion con-
ductivity. The above results reveal that am-Mg
(BH4)2
2NH3 possesses an apparent electro-
chemical stability window of 0–1.4 V with the
help of protective in-situ formed SEI and CEI. A
comparison on conductivities and stabilities of
relative solid Mg electrolytes is given in
Table S2, Supporting Information.[16–19,22–28]
The cycling stability of am-Mg(BH4)2
2NH3-
based Mg symmetric cells is then assessed to
metric cell cycling at 0.05 mA cm 2
(14.13 lA) shows a flat over potential of 20–
30 mV in the initial 250 h, and gradually
becomes higher after 250 h, indicating a thickening of SEI. For the Mg
symmetric cell cycling at 0.1 mA cm 2 (28.26 lA), the galvanostatic
charge/discharge (GCD) curve is similar, but the over potential is
higher (30–50 mV). No short circuit is found after more than 600 h
cycling, suggesting that no apparent Mg dendrite forms during cycling
at low current densities (Figure S14, Supporting Information).
Furthermore, after increasing the current density to 1 mA cm 2,
the Mg symmetric cell encounters short circuit after 140 h (Figure S15,
Supporting Information). This implies that Mg dendrites can nucleate
and grow when the cycling current is enough high, which agrees with
literatures.[43] To determine the critical current density for dendrite
growth, we test the Mg symmetric cell at increasing current densities
(0.1 mA cm 2 increasement per cycle). As seen in Figure 5b, the over
potential rises with current density and short circuit occurs at
3.3 mA cm 2, corresponding to a critical current density of
3.2 mA cm 2 for am-Mg(BH4)2
2NH3. This value is higher than those
for liquid electrolytes, confirming the effective suppression of Mg den-
drites by solid electrolytes with higher shear modulus.
TiS2 is selected as the cathode material of am-Mg(BH4)2
2NH3
based all-solid-state Mg cells by taking the electrochemical stability
4 of 7 © 2022 The Authors. Energy & Environmental Materials published by
John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.

Figure 4. Cyclic voltammetry (CV) curves of Mg¦am-Mg(BH4)2
2NH3¦Mo cells at 75 °C within a) the
potential window of 0.2 to 1.4 V, b) open circuit voltage (OCV) to 0 V, and c) OCV to 1.4 V. d)
Electrochemical impedance spectroscopy of Mg¦am-Mg(BH4)2
2NH3¦Mo cells before and after CV
measurements.
Figure 5. Galvanostatic charge/discharge curves of Mg|am-Mg(BH4)2
2NH3|Mg cells at a) different that Mg vacancy migration is the main contribu-
constant current densities and b) increasing current densities at 75 °C.
into consideration.[44] Figure 6a shows the GCD curves of Mg|am-
Mg(BH4)2
2NH3|TiS2 cell in the voltage range of 0.2–1.4 V at
0.05 C (1 C = 250 mA g 1) and 75 °C. Three plateaus can be
observed in the discharge and charge profiles, corresponding to the
typical stepwise Mg-ion insertion into and extraction from the cath-
ode. The initial reversible specific capacity is 141 mAh g with a
coulombic efficiency of 91.7%, already comparable with that of
Energy Environ. Mater. 2022, 0, e12527
25750356, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12527 by Birla Institute of Technology & Science - Pilani, Wiley Online Library on [29/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
liquid electrolyte-based cells. This high
coulombic efficiency can be attributed to the
controllable irreversible Mg-ion insertion/ex-
traction and formation of protective inter-
phases. In the following cycles, the specific
capacity decreases with the coulombic effi-
ciency further increases. The cycling perfor-
mance of Mg|am-Mg(BH4)2
2NH3|TiS2 cell at
0.05 C and 75 °C is shown in Figure 6b. The
reversible specific capacity fades from 141 to
70 mAh g 1 quickly in the initial 10 cycles,
and then maintains at above 50 mAh g 1 in
the following 15 cycles with coulombic effi-
ciencies of close to 100%. The capacity decay
may be ascribed to the structural degradation
of the cathode,[45] and we will further improve
the cycling stability by rational design of elec-
trodes in future works.
Figure 6c shows the EIS spectra of Mg|am-
Mg(BH4)2
2NH3|TiS2 cell before and after
cycling, which can be well fitted using equiva-
lent circuit and parameters shown in Table S3,
Supporting Information. The interphase resis-
tance increases from 1843 to 3457 Ω after the
first cycle and then slightly increases to 4032 Ω
after the following nine cycles, indicating that
interphase forms in the first cycle and prevents
the further degradation of the electrode/elec-
trolyte interface.[46] Figure 6d shows the GCD
curves of am-Mg(BH4)2
2NH3 based Mg||TiS2
cell at 0.05, 0.2, 0.5 C, and 75 °C. The voltage
hysteresis increases with current density, result-
ing in an apparent reduction in reversible speci-
fic capacity. The above results prove that the
high conductivity and excellent electrochemical
stability of Mg(BH4)2
2NH3 can enable the
cycling of all-solid-state Mg||TiS2 cells at 75 °C.
3. Conclusion
In conclusion, am-Mg(BH4)2
xNH3 (x = 1, 2,
3) are successfully prepared by high-energy ball
milling of c-Mg(BH4)2 and Mg(BH4)2
6NH3.
Among them, am-Mg(BH4)2
2NH3 is found to
exhibit the best Mg-ion conduction properties,
as a high conductivity of 5 9 10 4 S cm 1 at
75 °C with a Mg-ion transference number of
0.95 can be obtained. DFT calculations reveal
tor to the Mg-ion conduction, and the migration
energy barriers for Mg(BH4)2
2NH3 are lower
than those of c-Mg(BH4)2 and Mg(BH4)2
NH3. The apparent electro-
chemical stability window of am-Mg(BH4)2
2NH3 reaches 0–1.4 V
with the help of protective and conductive SEI and CEI. The Mg sym-
metrical cells based on am-Mg(BH4)2
2NH3 can cycled at
0.05 mA cm 2 for 710 h, and the critical current density is
1
3.2 mA cm 2. Moreover, am-Mg(BH4)2
2NH3 enables the cycling of
all-solid-state Mg||TiS2 cells, which shows a reversible specific capacity
5 of 7 © 2022 The Authors. Energy & Environmental Materials published by
John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.
 25750356, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12527 by Birla Institute of Technology & Science - Pilani, Wiley Online Library on [29/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Arbin BT2000. The conductivities and activation
energy were calculated from the EIS of Mo|elec-
trolyte|Mo cells (Equations S1 and S2, Supporting
Information). The electronic transference number
was calculated according to the DC polarization
of Mo|electrolyte|Mo cells at 1 V. The Mg-ion
transference number was calculated according to
the DC polarization of Mg|electrolyte|Mg cells at
10 mV and EIS before and after polarization
(Equation S3, Supporting Information).
First-principle calculations: Density functional
theory calculations were implemented in the
Vienna ab initio simulation package with the
projector-augmented wave construction for the
pseudopotential.[47,48] Exchange and correlation
were treated in the generalized gradient approxi-
mation of Perdew-Burke-Ernzerhof.[49] The cutoff
energy was set to 500 eV to attain sufficient
accuracy. A 3 9 3 9 3 k point mesh and the
k-point sampling scheme of Monkhorst-Pack
were applied in all calculations. The convergence
criterion of self-consistent total energy was
<10 5 eV per cell, and forces on each atom con-
verged to be below 0.01 eV
A 1. The lattice vol-
ume and shape were allowed to change. The
climbing-image nudged elastic band method was
applied for the ion migration pathways, and all
atoms were allowed to fully relax.[50] The
vacancy formation energy and interstitial forma-
Figure 6. a) Galvanostatic charge/discharge (GCD) curves of Mg|am-Mg(BH4)2
2NH3|TiS2 cell at 0.05 C and
tion energy were calculated from the total ener-
75 °C. b) Cycling performance of Mg|am-Mg(BH4)2
2NH3|TiS2 cell at 0.05 C and 75 °C. c) Electrochemical
gies of the simulation cell with and without
impedance spectroscopy of Mg|am-Mg(BH4)2
2NH3|TiS2 cell before and after different cycles. d) GCD curves
vacancy and interstitial.[51]
of Mg|am-Mg(BH4)2
2NH3|TiS2 cells at different current densities at 75 °C.

of 141 mAh g 1 with a coulombic efficiency of 91.7% at the first cycle Acknowledgements
and maintains at above 50 mAh g 1 in the following 25 cycles.
Y.P. and Z.N. contributed equally to this work. The authors gratefully acknowl-
edge the support of the National Natural Science Foundation of China
(51971146, 51971147, 52171218 and 52271222), the Shanghai Municipal Science
4. Experimental Section and Technology Commission (21010503100), the Major Program for the Scientific
Research Innovation Plan of Shanghai Education Commission (2019-01-07-00-07-
Preparation of materials: Mg(BH4)2 (c phase, 95%; Sigma-Aldrich) and NH3 E00015), the Shanghai Outstanding Academic Leaders Plan, the Guangxi Key Lab-
(99.9%; Sinopharm) was used as received without further purification. Mg oratory of Information Materials (Guilin University of Electronic Technology,
(BH4)2
6NH3 was synthesized by heating Mg(BH4)2 under 6 bar NH3 at 105 °C 201017-K), the Shanghai Rising-Star Program (20QA1407100), and the General
for 12 h. Mg(BH4)2
xNH3 (x = 1, 2 and 3) samples were prepared by high-energy Program of Natural Science Foundation of Shanghai (20ZR1438400).
ball milling the mixtures of Mg(BH4)2 and Mg(BH4)2
6NH3 with molar ratios of
5:1, 2:1, and 1:1 at 500 rpm for 24 h, respectively (Nanda Instrument QM-3SP2
mill, ZrO2 jar and ball, ball-to power ratio of 80:1). All sample handling is per- Conflict of Interest
formed in a glovebox (MBRAUN 200B) with H2O and O2 amount <0.1 ppm.
Characterizations: X-ray diffraction measurements were performed on Rigaku The authors declare no conflict of interest.
Ultima IV at a scan rate of 5° min 1 using a sealed sample holder. Raman spectra
were achieved by Bruker Optics Senterra R200-L with a laser wavelength of
532 nm using a sealed quartz holder. TEM observations were performed on JEOL Supporting Information
JEM-2100HR. The sample was dispersed on a carbon-coated Cu grid after hand-
grinding and then transferred under Ar atmosphere. The phase transition was Supporting Information is available from the Wiley Online Library or from
investigated by using DSC (Netzsch Polyma 214) from 50 °C to 350 °C with a the author.
scan rate 10 °C min 1 under Ar atmosphere.
Measurements: All-solid-state cells were assembled using homemade Swagelok
type dies, which can work under 100 MPa stack pressure (Figure S16, Supporting
Information). The electrolyte pellets with a diameter of 10 mm and a thickness
Keywords
of 0.5 mm were made by pressing the target materials under 100 MPa (Fig- all-solid-state Mg batteries, amorphization, Mg borohydride ammoniate, Mg
ure S17, Supporting Information). For different measurements, different elec- vacancy migration, solid electrolyte
trodes were used, that is Mo foil (ThermoFisher, 10 mm diameter), Mg foil
(99.9%, Sinopharm, 6 mm diameter, 0.2 mm thickness, 5 mg), and TiS2-based
Received: May 10, 2022
cathode (10 mm diameter, 1 mg, 40 wt% TiS2, 99.9%, Sigma-Aldrich, 60 wt%
Revised: September 5, 2022
am-Mg(BH4)2
2NH3).
Published online: September 6, 2022
Electrochemical impedance spectroscopy, DC polarization, and CV were con-
ducted on Gamry Interface 1000E. GCD measurements were performed using

Energy Environ. Mater. 2022, 0, e12527 6 of 7 © 2022 The Authors. Energy & Environmental Materials published by
John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.

[1] F. Liu, T. Wang, X. Liu, L. Z. Fan, Adv. Energy Mater. 2021, 11, 2000787.
[2] P. Saha, M. K. Datta, O. I. Velikokhatnyi, A. Manivannan, D. Alman, P.
N. Kumta, Prog. Mater. Sci. 2014, 66, 1.
[3] H. Fan, X. Zhang, Y. Zhao, J. Xiao, H. Yuan, G. Wang, Y. Lin, J. Zhang, L.
Pan, T. Pan, Y. Liu, Y. Zhang, Energy Environ. Mater. 2022, DOI: 10.
1002/eem2.12327.
[4] H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinsky, N. Pour, D. Aurbach,
Energy Environ. Sci. 2013, 6, 2265.
[5] R. Deivanayagam, B. J. Ingram, R. Shahbazian-Yassar, Energy Storage
Mater. 2019, 21, 136.
[6] J. Muldoon, C. B. Bucur, A. G. Oliver, T. Sugimoto, M. Matsui, H. S.
Kim, G. D. Allred, J. Zajicek, Y. Kotani, Energy Environ. Sci. 2012, 5,
5941.
[7] C. Liebenow, J. Appl. Electrochem. 1997, 27, 221.
[8] R. E. Doe, R. Han, J. Hwang, A. J. Gmitter, I. Shterenberg, H. D. Yoo, N.
Pour, D. Aurbach, Chem. Commun. 2014, 50, 243.
[9] O. Tutusaus, R. Mohtadi, T. S. Arthur, F. Mizuno, E. G. Nelson, Y. V.
Sevryugina, Angew. Chem. Int. Ed. 2015, 54, 7900.
[10] B. Li, R. Masse, C. Liu, Y. Hu, W. Li, G. Zhang, G. Cao, Energy Storage
Mater. 2019, 22, 96.
[11] B. McAllister, L. Kyne, T. Schon, D. Seferos, Joule 2019, 3, 620.
[12] Y. Zhang, H. Geng, W. Wei, J. Ma, L. Chen, C. C. Li, Energy Storage
Mater. 2019, 20, 118.
[13] J. Lin, L. Lin, S. Qu, D. Deng, Y. Wu, X. Yan, Q. Xie, L. Wang, D. Peng,
Energy Environ. Mater. 2022, 5, 133.
[14] Y. Gao, A. M. Nolan, P. Du, Y. Wu, C. Yang, Q. Chen, Y. Mo, S. H. Bo,
Chem. Rev. 2020, 120, 5954.
[15] P. Jaschin, Y. Gao, Y. Li, S. H. Bo, J. Mater. Chem. A 2020, 8, 2875.
[16] M. Adamu, G. M. Kale, J. Phys. Chem. C 2016, 120, 17909.
[17] T. Yamanaka, A. Hayashi, A. Yamauchi, M. Tatsumisago, Solid State Ion-
ics 2014, 262, 601.
[18] P. Canepa, S. H. Bo, G. Sai Gautam, B. Key, W. D. Richards, T. Shi, Y.
Tian, Y. Wang, J. Li, G. Ceder, Nat. Commun. 2017, 8, 1759.
[19] S. Higashi, K. Miwa, M. Aoki, K. Takechi, Chem. Commun. 2014, 50,
1320.
[20] F. Cuevas, M. B. Amdisen, M. Baricco, C. E. Buckley, Y. W. Cho, P. de
Jongh, L. M. de Kort, J. B. Grinderslev, V. Gulino, B. C. Hauback, M.
Heere, T. Humphries, T. R. Jensen, S. Kim, K. Kisu, Y.-S. Lee, H.-W. Li, R.
Mohtadi, K. T. Møller, P. Ngene, D. Noreus, S. Orimo, M. Paskevicius,
M. Polanski, S. Sartori, L. N. Skov, M. H. Sørby, B. C. Wood, V. A. Yartys,
M. Zhu, M. Latroche, Prog. Energy 2022, 4, 032001.
[21] Y. Pang, Y. Liu, J. Yang, S. Zheng, C. Wang, Mater. Today Nano 2022,
18, 100194.
[22] R. Le Ruyet, R. Berthelot, E. Salager, P. Florian, B. Fleutot, R. Janot, J.
Phys. Chem. C 2019, 123, 10756.
[23] R. Le Ruyet, B. Fleutot, R. Berthelot, Y. Benabed, G. Hautier, Y. Fil-
inchuk, R. Janot, ACS Appl. Energy Mater. 2020, 3, 6093.
[24] E. Roedern, R. S. Kuhnel, A. Remhof, C. Battaglia, Sci. Rep. 2017, 7, 46189.
Energy Environ. Mater. 2022, 0, e12527 7 of 7
25750356, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12527 by Birla Institute of Technology & Science - Pilani, Wiley Online Library on [29/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
[25] K. Kisu, S. Kim, M. Inukai, H. Oguchi, S. Takagi, S.-I. Orimo, ACS Appl.
Energy Mater. 2020, 3, 3174.
[26] Y. Yan, W. Dononelli, M. Jorgensen, J. B. Grinderslev, Y. S. Lee, Y. W. Cho,
R. Cerny, B. Hammer, T. R. Jensen, Phys. Chem. Chem. Phys. 2020, 22, 9204.
[27] Y. Yan, J. B. Grinderslev, M. Jogensen, L. N. Skov, J. Skibsted, T. R. Jen-
sen, ACS Appl. Energy Mater. 2020, 3, 9264.
[28] Y. Yan, J. Grinderslev, T. Burankova, S. Wei, J. Embs, J. Skibsted, T. Jen-
sen, J. Phys. Chem. Lett. 2022, 13, 2211.
[29] Q. Wang, H. Li, R. Zhang, Z. Liu, H. Deng, W. Cen, Y. Yan, Y. Chen,
Energy Storage Mater. 2022, 51, 630.
[30] Y. Pang, J. Pan, J. Yang, S. Zheng, C. Wang, Electrochem. Energy Rev.
2021, 4, 1.
[31] O. Tutusaus, R. Mohtadi, N. Singh, T. S. Arthur, F. Mizuno, ACS Energy
Lett. 2017, 2, 224.
[32] Y. Yang, Y. Liu, Y. Li, M. Gao, H. Pan, Chem. Asian J. 2013, 8, 476.
[33] G. Soloveichik, J.-H. Her, P. W. Stephens, Y. Gao, J. Rijssenbeek, M.
Andrus, J.-C. Zhao, Inorg. Chem. 2008, 47, 4290.
[34] O. Zavorotynska, A. El-Kharbachi, S. Deledda, B. C. Hauback, Int. J.
Hydrog. Energy 2016, 41, 14387.
[35] Y. Yang, Y. Liu, H. Wu, W. Zhou, M. Gao, H. Pan, Phys. Chem. Chem.
Phys. 2014, 16, 135.
[36] Y. Filinchuk, B. Richter, T. R. Jensen, V. Dmitriev, D. Chernyshov, H.
Hagemann, Angew. Chem. Int. Ed. 2011, 50, 11162.
[37] S. Zhao, B. Xu, N. Sun, Z. Sun, Y. Zeng, L. Meng, Int. J. Hydrog. Energy
2015, 40, 8721.
[38] Y. Limoge, “Diffusion in Amorphous Materials.” Diffusion in Materials,
Springer, Dordrecht 1990, pp. 601–24.
[39] J. L. Souquet, Ann. Rev. Mater. Sci. 1981, 11, 211.
[40] V. Gulino, A. Wolczyk, A. Golov, R. Eremin, M. Palumbo, C. Nervi, V.
Blatov, D. Proserpio, M. Baricco, Inorg. Chem. Front. 2020, 7, 3115.
[41] F. Han, Y. Zhu, X. He, Y. Mo, C. Wang, Adv. Energy Mater. 2016, 6,
1501590.
[42] F. Lu, Y. Pang, M. Zhu, F. Han, J. Yang, F. Fang, D. Sun, S. Zheng, C.
Wang, Adv. Funct. Mater. 2019, 29, 1809219.
[43] R. Davidson, A. Verma, D. Santos, F. Hao, C. Fincher, S. Xiang, J. Van
Buskirk, K. Xie, M. Pharr, P. P. Mukherjee, S. Banerjee, ACS Energy Lett.
2019, 4, 375.
[44] X. Sun, P. Bonnick, L. F. Nazar, ACS Energy Lett. 2016, 1, 297.
[45] Y. Pang, X. Wang, X. Shi, F. Xu, L. Sun, J. Yang, S. Zheng, Adv. Energy
Mater. 2020, 10, 1902795.
[46] M. Zhu, Y. Pang, F. Lu, X. Shi, J. Yang, S. Zheng, ACS Appl. Mater. Inter-
faces 2019, 11, 14136.
[47] P. E. Blochl, O. Jepsen, O. Andersen, Phys. Rev. B 1994, 49, 16223.
[48] G. Kresse, J. Furthm€uller, Phys. Rev. B 1996, 54, 11169.
[49] J. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.
[50] G. Henkelman, B. P. Uberuaga, H. Jonsson, J. Chem. Phys. 2000, 113, 9901.
[51] M. A. Tschopp, M. F. Horstemeyer, F. Gao, X. Sun, M. Khaleel, Scr.
Mater. 2011, 64, 908.
© 2022 The Authors. Energy & Environmental Materials published by
John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.