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Electrochemical Fixation of Carbon Dioxide in Molten Salts
on Liquid Zinc Cathode to Zinc@Graphitic Carbon Spheres
for Enhanced Energy Storage
Teng Lv, Juanxiu Xiao,* Wei Weng, and Wei Xiao*
Fixation of carbon dioxide into advanced energy materials is an ideal protocol
to address challenges in energy and environmental sustainability, with the
efficiency of CO2 fixation and the functionality of derived materials being
the key-enabling factors. Herein, using a liquid zinc cathode for CO2 fixa-
tion in molten salts, CO2 is electrochemically converted to graphitic carbon
shells over spherical Zn cores, namely, Zn@C. The liquid Zn serves as a
depolarizer to facilitate the reduction of CO2, and also a soft template to
direct the generation of core–shell Zn@C spheres. Density functional theory
calculations reveal that the coexisting Zn can enlarge the interlayer gap of
graphitic carbon and induce a strong electronic interaction with AlCl4−. Such
a strong coupling between Zn and carbon hence offers an enhanced energy
storage capability of the Zn@C. The present study provides suggestions for
enhancing efficiency of CO2 fixation and value-added utilization of nonferrous
metals.
1. Introduction
Excessive emission of carbon dioxide (CO2) is a threat to the
ecological balance.[1–5] CO2 is also an exploitable carbon and
oxygen resource.[6–12] Fixation of CO2 into valuable chemicals
could simultaneously realize carbon reduction and reutiliza-
tion of CO2.[6,13] For example, high-efficiency fixation of CO2
T. Lv, Dr. W. Weng, Prof. W. Xiao
School of Resource and Environmental Sciences
Hubei International Scientific and Technological Cooperation
Base of Sustainable Resource and Energy
Wuhan University
Wuhan 430072, P. R. China
E-mail: 00030042@whu.edu.cn
Prof. J. X. Xiao
State Key Laboratory of Marine Resource Utilization in South China Sea
Hainan University
No. 58, Renmin Avenue, Haikou, Hainan 570228, P. R. China
E-mail: xiaojuanxiu@hainanu.edu.cn
Dr. W. Weng, Prof. W. Xiao
College of Chemistry and Molecular Sciences
Hubei Key Laboratory of Electrochemical Power Sources
Wuhan University
Wuhan 430072, P. R. China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202002241.
DOI: 10.1002/aenm.202002241
Adv. Energy Mater. 2020, 2002241 2002241  (1 of 11)
to epoxides is realized in ionic liquids by
Sun and co-workers.[14,15] Fixation and uti-
lization of CO2 is also elaborately explored
via designing the metal–CO2 batteries by
Ding and co-workers.[16] Fixation of CO2
into functional carbonaceous materials
by capture and electrochemical reduction
of CO2 in molten salts has many advan-
tages.[6,17–19] CO2 shows a high solubility
in molten salts, guaranteeing a high-
flux uptake rate for a direct and deep
removal of CO2 from atmosphere and
industrial flue gas.[6] The wide electro-
chemical window of molten salt electro-
lytes promises a high current efficiency
of the electrochemical reduction of CO2
in molten salts.[6,20–24] The high-temper-
ature environment of inorganic molten
salts brings about enhanced mass transfer
and facilitated reaction kinetics, enab­
ling an appealing conversion rate of CO2 free of any precious
catalysts.[6,14,15] Molten salts possess a high heat capacity, which
means the heat required by the molten salt fixation of CO2 can
be supplied by solar-thermal systems.[17] The decomposition
voltage of CO2-capture-generated CO32− in molten salts is lower
than 2.0  V (1.3  V for Li2CO3, 1.6  V for Na2CO3, and 1.8  V for
K2CO3 at 500 °C), therefore the electricity for the conversion of
CO2 in molten salts can be supplied by solar photovoltaic sys-
tems.[17] Finally, oxygen in CO2 can simultaneously be released
as anodic O2, which is of prime implications on future colony
on Mars.[6]
One of the major challenges for the electrochemical fixation
of CO2 in molten salts is the insufficient functionality of the
deposited carbon on cathode.[6] Amorphous and disordered
carbon is commonly obtained by electrochemical conversion
of CO2 in molten salts, which contradicts with the demands
of application devices for carbonaceous materials with high
graphitization degree.[6] For example, aluminum-ion (Al-ion)
battery (AIB) possesses the merits of low cost, high volu-
metric capacity, and high safety. Many cathode materials are
reported for Al-ion batteries, including carbon-based mate-
rials, metal sulfides, and V2O5.[25–27] For carbon-based mate-
rials, the carbon with higher graphitization degree commonly
possesses better performance for reversible Al storage.[26,27] In
this regard, pioneering works were conducted by Lu and co-
workers.[7,28–33] In their strategy, a highly porous 3D graphene
foam is used as the cathode for rechargeable Al-ion batteries,
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Figure 1.  Illustration on the electrochemical fixation of CO2 in molten
salts by using a liquid Zn cathode. CO2 is converted to anodic O2 and
cathodic Zn@C on the liquid Zn cathode. Zn@C can act as the positive
electrode for Al-ion battery.
enabling a high capacity of ≈123  mAh g−1 at 5 A g−1, a high
Coulombic efficiency of more than 98%, and a long-term sta-
bility up to 10 000 cycles as well as a high rate performance.[28]
Also, Gao and co-workers designed a special “trihigh tricon-
tinuous” graphene film cathode, presenting a high capacity of
≈120 mAh g−1 at an ultrahigh current density of 400 A g−1.[26]
The reduction of highly stable CO2 is thermodynamically
uphill and kinetically sluggish, causing high energy consump-
tion and involvement of complicated/expensive catalysts. Fixa-
tion of carbon dioxide into advanced energy materials with
accelerated CO2 conversion and enhanced functionality of
derived products is hence of urgency and importance, which,
however, remains a challenge hitherto. A fast reduction pro-
cess can hopefully be realized by using liquid metals as cath-
odes because liquid metals can not only act as the depolarizer
via the alloying effect, but also enhance the mass transfer on
the electrolyte–electrode interfaces due to the flowable charac-
teristics.[34,35] Nevertheless, using the liquid metals as cathodes
for the electrochemical fixation of CO2 in molten salts still
remains to be explored.
Herein, a liquid zinc cathode is introduced to the electro-
chemical fixation of CO2 in molten salts, to simultaneously
accelerate CO2 conversion and enhance the functionality of
derived materials. Specifically, the unique interface between
the liquid Zn and the molten salt results in self-template
formation of Zn encapsulated inside the graphitic hollow
carbon shell (Zn@C) in the cathode and O2 evolution on
the anode (Figure  1). When evaluated as the active material
of positive electrode for Al-ion battery, the obtained Zn@C
shows enhanced Al storage capability compared with the
hollow carbon shell. The underlying mechanism of the liquid-
Zn strategy on accelerating CO2 fixation and enhancing
functionality of the fixation product is rationalized based
on experimental investigation and density functional theory
(DFT) calculations. The present study, we hope, could form
a solid basis on efficient fixation of carbon dioxide into
advanced energy materials and value-added utilization of
massive nonferrous metals.
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2. Results and Discussion
2.1. Morphology and Composition
Potentiostatic electrolysis was conducted at −0.9  V versus Ag/
Ag2SO4 for 3 h in the Li2CO3–Na2CO3–K2CO3 molten salt at
450  °C,  with the liquid Zn as the working electrode (cathode)
and a platinum-coated titanium plate as the counter elec-
trode (anode). The X-ray diffraction (XRD) pattern (red line in
Figure  2a), Raman spectrum (red line in Figure  2b and inset
in Figure  2b), and X-ray photoelectron spectrometer (XPS)
spectra (see Zn 2p spectrum in the left side and C ls spectrum
in the right side of Figure  2c) all prove the coexistence of Zn
and C in the cathodic Zn@C.[22,35,36] In Figure  2a, the broad
peak located at 23° is ascribed to the (002) crystal plane of gra-
phitized carbon (JCPDS No. 01-0646). The G band in Raman
spectrum is the common feature of graphitic materials while
D band is the indicator of defects in graphitic carbon.[22] The
stronger G peak than that of D peak in the Raman spectrum of
Zn@C also suggests the graphitization (red line in Figure 2b).
The core–shell morphology is certified by the field emission
scanning electron microscopy (FESEM) and transmission elec-
tron microscopy (TEM) results. The spheres (Figure  2d) with
the diameter in 100–200  nm (Figure  2e) are observed in the
FESEM results, which are revealed to be core–shell structure
by TEM image (Figure  2f). The core–shell structure consists
of a metallic Zn core (≈108 nm in diameter) and a graphitized
carbon shell (≈23 nm in thickness), as shown in Figure 2g. The
interplanar distances of 3.4 Å in the shell and 2.1 Å in the core
in the high-resolution TEM image (Figure  2h) are ascribed to
the crystal planes of graphitic carbon (002) and Zn (101).[22,35,36]
The elements distributions also validate the core–shell Zn@C
structure, as confirmed by the separated location of Zn in the
core (Figure  2i–k) and carbon in the shell (Figure  2i,j,l). The
obtained core–shell Zn@C features a specific surface area of
160 m3 g−1 and a pore size centered at 4  nm (Figure S1, Sup-
porting Information).
O2 is released on the anode, as proven by the sharp increase
of O2 concentration to 410–540  ppm during electrolysis
(Figure 2m). CO2 in the flues gas is generated by the combus-
tion of coal in industrial factories such as the thermal power
plants. Therefore, the CO2-derived O2 on the anode can be
in-site used in these industrial factories for oxygen-enriched
combustion to enhance the combustion efficiency of fuels.[37]
In addition, the CO2-derived O2 can also be used for oxygen
therapy in hospital. Hence, the CO2 is electrochemically split
to O2 and graphitic carbon, which is assembled into core–shell
structured Zn@C spheres on the liquid Zn cathode.
2.2. Reaction Mechanism of CO2 Fixation
The time-dependent morphology evolution (Figure 3a–c) shows
that Zn@C spheres are extruded from the carbon flakes.
Within a short electrolysis period, e.g., 30 min (Figure 3a), only
plentiful humps on the carbon flakes are observed. Of note,
these Zn@C particles are partly buried inside the carbon flake
support and tend to detach from the support (Figure 3a). This
phenomenon implies that these nascent Zn@C particles are
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Figure 2.  Morphology and composition characterizations. a) XRD patterns, b) Raman spectra (inset is the spectrum in the range of 100–600 cm−1),
and c) XPS spectra (left: Zn 2p; right: C 1s) of Zn@C and hollow carbon shell (denoted as hollow carbon). d,e) FESEM images, f–h) TEM images,
i) HAADF-STEM image, and j–l) the corresponding elements distribution images of Zn@C. j) The mixed distribution of Zn and C, k) the distribution
of Zn, and l) the distribution of C. Panel (e) is the magnification of the squared area A in (d) and panel (h) is the magnification of the squared area B
in (g). m) Concentration change (ΔC) of anodic O2 during electrolysis. Sample Zn@C: graphitic carbon shell deposited on liquid Zn droplets using
a liquid Zn cathode; hollow carbon: carbon shell obtained by removing Zn in Zn@C after leaching in concentrated hydrochloric solution. Electrolysis
was conducted at −0.9 V versus Ag/Ag2SO4 for 3 h in 450 °C Li2CO3–Na2CO3–K2CO3 molten salt.

rooted out from the carbon flakes. Prolonging the electrolysis
to 120 min results in the growth of these small Zn@C spheres,
accompanied by the generation of newborn nascent particles
(Figure 3b). Prolonging the electrolysis to 180 min, surfaces of
the carbon flakes are fully covered by abundant Zn@C spheres
due to the continuous nucleation and growth, with the size of
Zn@C increasing to around 200  nm in diameter. The energy
dispersive X-ray spectroscopy (EDS) results also point to the
above path. As shown in Figure  3d, the Zn content in the
spherical area (point 1# in Figure  3b) is dominant (97.6 wt%),
containing a marginal content of carbon (2.2 wt%). The results
imply that metallic Zn (melting point: 419  °C)  is first gener-
ated and self-transformed to liquid droplets at the electrolysis
temperature (450  °C),  followed by the formation of core–shell
Zn@C structures due to the subsequent deposition of carbon.
The brighter areas in the backscatter electron image denote
heavier elements while the darker regions point to lighter ele-
ments.[38] Therefore, the bright cores and the darker shells/
flakes in the backscatter electron image in Figure 3e are attrib-
uted to the Zn and carbon, respectively, further depicting the
fact that the core–shell Zn@C spheres are closely attached to
the surface of carbon flakes.
Coupling between chemical and electrochemical reactions
contributes to the formation of core–shell structured Zn@C
spheres. By peering at the EDS results (Figure  3d) relating to
the carbon flake area (2# in Figure  3b), Zn (17.7 wt%) together

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Figure 3.  Understanding of the morphology evolution. FESEM images of cathode product after electrolysis at −0.9 V versus Ag/Ag2SO4 for a) 30 min,
b) 120 min, and c) 180 min. d) The EDS spectra of points 1# and 2# in (b). e) The backscatter electron image of sample in (c). f) The standard Gibbs
free energy changes of related reactions. g,h) The side-view and top-view images of the liquid Zn after soaking in molten salt for 3 h, respectively.
i–l) The cross-section SEM image in the surface area of (g) and the corresponding element distributions. m) The theoretical decomposition voltages
of Li2CO3, ZnO, and Li2O. n) Cyclic voltammogram (CV) curves recorded at 5 mV s−1 in 450 °C Li2CO3–Na2CO3–K2CO3 molten salt using a solid Mo
(black dashed line) or liquid Zn (red line) as the working electrode, home-made Ag/Ag2SO4 as the reference electrode, and platinum-coated titanium
plate as the counter electrode. o) Current efficiency and energy consumption for fixation of CO2 using the liquid Zn cathode or solid Mo cathode at
−0.9 V versus Ag/Ag2SO4 for 180 min as well as other solid cathodes in reported works.[18,19,43–47]

with O (22.2 wt%), instead of pure carbon, are detected. The chemical reaction between the liquid Zn cathode and the
results mean that the flakes are the mixture of carbon and ZnO, molten Li2CO3 (2Zn(l) + Li2CO3(l) = 2ZnO(s) + Li2O(l) + C(s)),
with the latter being as high as 39.9 wt%. The flake-like mix- as depicted by the negative Gibbs free energy change at the elec-
ture of ZnO and carbon is originated from the spontaneous trolysis temperature of 450 °C (Figure 3f). Such thermodynamic

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speculations are further validated by the experimental results in
Figure  3g–l, as shown by the black layer on the surface of Zn
bulks after soaking the Zn in Li2CO3–Na2CO3–K2CO3 molten
salt for 180 min (Figure 3g,h). The elements distributions reveal
that the black layer on the surface of soaked Zn consists of ZnO
and carbon, as manifested by the homogeneous distribution of
Zn and O as well as C on the upper surface (Figure 3i–l). Both
the decomposition voltages of ZnO and Li2CO3 are low (1.4 V for
ZnO and 1.3 V for Li2CO3; see Figure 3m) while that of Li2O is
much higher (2.5 V; see Figure 3m). The results mean that ZnO
and Li2CO3 can be easily electrochemically reduced to Zn and
carbon respectively, whereas the Li2CO3-reduction-generated
Li2O can keep stable and facilitate the capture of CO2 to
replenish the decomposed Li2CO3. Compared with the cyclic vol-
tammogram (CV) curve recorded on a solid molybdenum (Mo)
electrode, a new reduction peak at −0.75  V versus Ag/Ag2SO4
appears (Figure  3n) when using the liquid Zn as the working
electrode, again pointing to the surface oxidation of Zn by prior
chemical reaction and subsequent electrochemical reduction of
ZnO to Zn. Therefore, liquid Zn droplets are first formed by the
electrochemical reduction of ZnO, followed by the generation
of core–shell Zn@C spheres due to the subsequent deposition
of carbon from electrochemical reduction of Li2CO3. The gener-
ated Li2O during the above process facilitates the capture of CO2
to replenish the consumed Li2CO3, concomitantly directing to
the stable conversion of CO2 to Zn@C spheres.
In addition to direct the formation of core–shell structured
morphology, the liquid Zn droplets on the cathode–electrolyte
interfaces can also enhance the carbon deposition process.
In contrast to the solid Mo electrode (black dotted line in
Figure  3n), the liquid Zn cathode can enable the reduction of
CO2-capture-generated CO32− with a lower overpotential (that
is, more positive reduction potential indicated by the red line
in Figure 3n), suggesting that the liquid Zn can act as a depo-
larizer to facilitate the electrochemical fixation of CO2.[2,35,39]
Moreover, the liquid Zn cathode shows a larger current density
for the electrochemical reduction of CO32− over the solid Mo
electrode (Figure 3n), revealing that liquid Zn droplets can also
enhance the reaction kinetics by increasing the Zn–molten salt
interfacial area.[2,35,40] Furthermore, the flowable liquid Zn
can contribute to the real-time update of the reaction inter-
faces, also resulting in improved reaction kinetics.[2,39–42] Such
anticipations are verified by the increased current efficiency
and decreased energy consumption for the fixation of CO2 on
the liquid Zn cathode over the solid Mo cathode (Figure  3o).
In comparison to reported values for the solid cathodes in
molten salts (Figure  3o),[18,19,43–47] both the current efficiency
and the energy consumption also present more favorable values
on the liquid Zn cathode in this work, further manifesting
that the liquid Zn cathode can enable a more energy-efficient
electrochemical fixation of CO2 in molten salts.
Metallic Zn can act as the catalyst for promoting the
graphitization of deposited carbon on cathode.[2,42,48] Therefore,
the heterogeneous nucleation of carbon on the liquid Zn drop-
lets contributes to the formation of graphitized carbon shell on
the surfaces of Zn droplets, realizing the increase in graphiti-
zation degree and simultaneously assembling of sphere-like
structure. The optimized temperature and cathode potential for
the formation of Zn@C spheres are 450 °C and −0.9 V versus
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Ag/Ag2SO4, respectively. Thermodynamically, increasing the
temperature is disadvantageous for the formation of ZnO by
chemical reactions (that is, less negative values of Gibbs free
energy change at higher temperatures in Figure 3f). Less liquid
Zn droplets are formed during electrolysis at higher tempera-
tures, consequently restraining the heterogeneous nucleation
of carbon on the surfaces of liquid Zn. Therefore, less Zn@C
spheres are generated at higher temperatures (Figure S2, Sup-
porting Information). Easier formation of Zn@C at lower
temperatures also manifests the important role of Na2CO3
and K2CO3 because the melting point (395  °C)  of the ternary
Li2CO3–Na2CO3–K2CO3 salt (32:33:35 in weight ratio) is much
lower than that (720  °C)  of pure Li2CO3.[49] Hence, the func-
tion of the Na2CO3 and K2CO3 is to lower the melting point
of the molten salts, enabling the low-temperature CO2-fixation
process on the liquid Zn cathode and promoting the gen-
eration of Zn@C spheres. Electrolysis at temperatures lower
than 450  °C  is not conducted because of the insufficient con-
ductivity and viscosity of the molten salt electrolyte. Cathodic
potential can also determine the formation of Zn@C spheres.
When the cathodic potential is sufficiently negative, the rate-
determining step is the diffusion of reactive species rather than
the electrochemical polarization.[21] Diffusion of soluble CO32−
is much easier than that of solid ZnO, which means that the
co-reduction of CO32− and ZnO gradually turns to the domi-
nant reduction of CO32− with the shift of the cathode potential
toward the negative direction. Therefore, homogeneous
nucleation of carbon on the carbon flakes is dominant at large
negative potentials, leading to generation of less Zn@C spheres
(Figure S3, Supporting Information).
The coupling between chemical and electrochemical reac-
tions for the formation of graphitic carbon shell on the liquid
Zn droplets, namely, Zn@C spheres, is illustrated in Figure 4.
The one-end closed alumina tube containing a hole on the
side wall is used to contain the liquid Zn cathode (Figure  4a).
The detailed structure of the liquid Zn cathode is illustrated in
Figure 4b, in which the configuration on the molten salt–liquid
Zn interface is presented. The density of Zn (6.83  g cm−3),
deposited Zn@C (3.40 g cm−3), and the molten salt (2.06 g cm−3)
is in a descending order, enabling that Zn@C stays on the
interfaces without floating up or sinking down for stable nucle-
ation and growth. The density of Zn@C is calculated based
on 25 wt% Zn, which is determined by the thermogravimetric
analysis (Figure S4a, Supporting Information).[50] CO2 is first
captured by the O2− in molten salt to form soluble CO32−, fol-
lowed by the formation of Zn@C on the liquid Zn cathode and
O2 on anode.[6,17–19,48,51–54] Specifically, the chemical reaction
of “2Zn(l) + Li2CO3(l) = C(s) + 2ZnO(s) + Li2O(l)” (reaction 1
in Figure  4c) takes place prior to electrolysis, resulting in the
formation of ZnO particles and carbon flakes on the surface
of liquid Zn cathode. The ZnO particles embedded in carbon
flakes are then electrochemically reduced to liquid Zn drop-
lets via the reaction of “ZnO(s) + 2e− = Zn(l) + O2−” (reaction 2
in Figure 4c), which are extruded and separated from the carbon
flakes due to the surface tension and insolubility of Zn in
carbon at 450  °C  (Figure S5, Supporting Information).[2,35,39,42]
Finally, carbon deposition by electrochemical reduction of CO2-
capture-generated CO32− (CO32− + 4e− = C(s) + 3O2−, reaction 3
in Figure  4c) on the surface of liquid Zn droplets results in
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Figure 4.  a) Optical image of the one-end closed alumina tube. The closed end contains the liquid Zn and the hole on the side wall enables the free
flow of the molten salt. b) Structure illustration for the liquid Zn cathode. c) Illustration on the formation of core–shell structured Zn@C spheres on
carbon flakes.

the core–shell structured Zn@C spheres. The Zn core can
catalyze the graphitization of the carbon shell in the Zn@C
spheres.[42,48]
Notably, the above-mentioned chemical and electrochem-
ical reactions take place concurrently, real-timely updating
the Zn–molten salt interfaces and incessantly generating the
Zn@C spheres on carbon flakes. At the same time, O2− in CO2-
capture-generated CO32− was released and discharged to O2 on
the surfaces of the inert anode (Figure 2m). Consequently, the
coupling between chemical and electrochemical reactions as
well as the CO2 capture process contributes to the fixation of
CO2 to the carbon in Zn@C spheres on the liquid Zn cathode
and O2 on anode. Electrochemical conversion of CO2 to CO
and O2 can also be realized by elevating the temperature of
molten salts to more than 900 °C, which is reported in previous
works.[55,56] Calculations reveal that the coupling between chem-
ical and electrochemical reactions are more difficult to take
place on other commonly used pure liquid metals (Figure S6,
Supporting Information). Using low-melting-point alloys rather
than pure metals as cathodes is a promising solution to obtain
similar core–shell products during the electrochemical fixation
of CO2 in molten salts.
2.3. Al-Ion Battery Performance and DFT Calculations
Performance tests show that the existence of Zn in the Zn@C
enhances the ability of the carbon shell for energy storage. For
comparison, the ability of the hollow carbon and the commer-
cial Zn powder (analytical reagent, provided by Sinopharm
Chemical Reagent Co., Ltd.) for aluminum storage were also
tested. The hollow carbon shells were obtained by thoroughly
leaching the Zn@C spheres in concentrated hydrochloric acid
to remove the Zn cores (Figure S7, Supporting Information).
The XRD pattern (Figure  2a), Raman spectra (Figure  2b), and
XPS spectra (Figure 2c) all prove the complete removal of Zn.
Without extra mention, the Zn content in Zn@C is 25 wt%
(Figure S4, Supporting Information), which is denoted as

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Figure 5.  a) Charge/discharge curves at 200 mA g−1, b) CV curves of Zn@C and the hollow carbon shell (denoted as hollow carbon), c) capacities of
“Zn@C (25 wt% Zn)” and “Zn@C (6.4 wt% Zn)” at 500 mA g−1, hollow carbon at 500 mA g−1, and metallic Zn powder at 100 mA g−1 as well as the
Coulombic efficiency of “Zn@C (25 wt% Zn).” d) Adsorption and intercalation energies of Zn-free graphite (002) plane (denoted as hollow carbon)
and Zn-containing graphite (002) plane (denoted as Zn@C). e) Optimized structures of AlCl4−-intercalated Zn@C (left) and AlCl4−-intercalated hollow
carbon (right). “Zn@C (25 wt% Zn)” and “Zn@C (6.4 wt% Zn)” mean the samples containing 25 wt% Zn and 6.4 wt% Zn, respectively.

“Zn@C (25 wt% Zn)” in Figure 5a–c. Also, Zn@C containing
6.4 wt% Zn is obtained by controlling the acid-leaching time
(see experimental details and Figure S4 in the Supporting
Information), which is denoted as “Zn@C (6.4 wt% Zn)” in
Figure 5a–c for comparison.
As shown in Figure 5a, the capacity fading in the discharge
curves of “Zn@C (25 wt% Zn)” is small from the 2nd to 450th
cycle, whereas the value of hollow carbon shell decreases sharply
from 100 to 30 mAh g−1. The better performance of “Zn@C
(25 wt% Zn)” for energy storage is also manifested by the larger
reduction current and more obvious reduction peak at 1.25  V
versus Al/AlCl4− in the CV curves of “Zn@C (25 wt% Zn)”
over the hollow carbon shell in Figure  5b. The Zn@C also
shows much higher capacity than that of the hollow carbon.
Specifically, “Zn@C (25 wt% Zn)” remains ≈90 mAh g−1
after 450 cycles while the hollow carbon drops dramatically to
30 mAh g−1 at 200  mA g−1 (Figure S8, Supporting Informa-
tion). Moreover, the “Zn@C (25 wt% Zn)” shows much more
appealing long-term stability than that of the hollow carbon
shell, as manifested in Figure  5c by the negligible capacity
fading of “Zn@C (25 wt% Zn)” after 3000 cycles at 500 mA g−1
and a high Coulombic efficiency of ≈100%. In comparison to
Zn@C and the hollow carbon, the capacity fading is much more
obvious for the metallic Zn powder (Figure S9a, Supporting
Information), remaining only 15 mAh g−1 after 279 cycles at
100 mA g−1 (Figure 5c). Such a low capacity of the metallic Zn
indicates that the enhanced ability of Zn@C for aluminum
storage is caused by the synergy between the carbon shell and
the metallic Zn core, rather than the additional capacity for
aluminum storage contributed by the metallic Zn. Although
the performance of obtained Zn@C is still much lower than
the state-of-the-art carbon materials in aluminum storage, e.g.,
≈120 mAh g−1 at 5 A g−1 reported by Lu and co-workers,[28] the
application of CO2-derived carbon composites for aluminum
storage and the promotion of Zn core for the aluminum storage
of the carbon shell are revealed, which can provide insights in
value-added conversion of CO2 to functional materials. Of note,
the usage of the liquid Zn cathode can provide a more energy-
efficient electrochemical fixation of CO2 in molten salts, also
shedding new lights on the high-efficiency conversion of CO2.
The capacity of Zn@C spheres for energy storage can be
further improved by increasing the graphitization degree of
carbon or optimizing the Zn content in Zn@C. Increased
graphitization degree of carbon contributes to higher inter-
calation-induced capacity in aluminum storage. The inter-
calation capacity of Zn@C is not high, as evidenced by the

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broad reduction peak in CV curves (Figure  5b), which is a
typical characteristic of capacitive processes.[57] Therefore,
restraining the capacitive process by increasing the graphiti-
zation degree of CO2-derived carbon is one way to further
enhance the aluminum storage of Zn@C. It is acknowledged
that the graphitization of the CO2-derived carbon herein
needs to be further increased. The strategy on tailoring the
microstructure of the derived carbon during electrochemical
reduction of CO2 in molten salts have been well addressed,[6]
with higher graphitization of carbon occurring in the pres-
ence of liquid metal (the herein protocol), sulfur oxides,[18,59]
elevated temperature,[58,59] higher overpotential, and metallic
catalysts[8,58] Another way to further improve the capacity is to
optimize the content of Zn in Zn@C. As shown in Figure 5c
and Figure S9b in the Supporting Information, the “Zn@C
(6.4 wt% Zn)” possesses much higher capacity than “Zn@C
(25 wt% Zn),” revealing that optimizing the Zn content is an
effective way to further enhance the energy storage ability of
CO2-derived carbon. Excess content of Zn is not beneficial for
enlarging the overall capacity of Zn@C because of the low
capacity of pure Zn powder (Figure  5c). Compared with the
capacity calculated based on the total mass of Zn and C in
Zn@C, the capacity calculated based on the mass of only
carbon in Zn@C is much higher (Figure S8, Supporting
Information), also implying the influence of Zn content in
overall capacity. Appropriate content of Zn can improve the
aluminum storage of carbon in Zn@C by inducing the syn-
ergy effect between Zn and C. However, such a synergy effect
can only be induced by the Zn atoms located in the core–shell
interfaces (denoted as the transition layer in Figure S10 in
the Supporting Information) because of the intimate contact
between the two elements in this region. Therefore, opti-
mizing the Zn content in the core to construct the yolk–shell
Zn@C structure can remove the excessive inactive Zn and
remain the active Zn layer in the transition layer at the same
time, being an applausive way to further improve the capacity
of Zn@C in energy storage.
DFT calculations reveal that the Zn enlarges the interplanar
distance of graphitic carbon, and promotes both the adsorp-
tion and intercalation of AlCl4−. The coexistence of Zn and C
occurs in the interfaces of Zn core and carbon shell (denoted
as the transition layer in Figure S10 in the Supporting Informa-
tion), implying the intercalation of Zn atoms within the layers
of graphitic carbon. Therefore, the Zn-intercalated graphite
(002) is constructed as a simplified structure of Zn@C to calcu-
late the intercalative energy of AlCl4− in Zn@C spheres. More
details for the calculation steps and structure constructions are
shown in Figures S11–S19 and Tables S1–S5 in the Supporting
Information. As shown in Figure 5d, the adsorption energy of
AlCl4− on the Zn-containing graphite (denoted as Zn@C) is
−3.45 eV, much higher than that (−1.83 eV) on Zn-free graphite
(denoted as hollow carbon), suggesting the stronger adsorption
of AlCl4− in the former case. Moreover, the intercalation energy
of AlCl4− in Zn@C (−3.73 eV) is larger than that (−2.75 eV) in
hollow carbon, meaning easier intercalation of AlCl4− in the
former case.[24,60–63] The strong interaction between Zn and
AlCl4− is likely one of the reasons for the above results, which
is proved by the obvious tendency of electron transfer from
Zn to Cl in AlCl4− (right side in Figure S20 in the Supporting
Adv. Energy Mater. 2020, 2002241 2002241  (8 of 11)
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Information).[24,60–63] Instead, the electronic interaction between
AlCl4− and graphite in hollow carbon is much weaker (left side
in Figure S20 in the Supporting Information). Additionally,
both the total density of states (TDOS) and projected density
of states (PDOS) show the strong interaction between Zn and
AlCl4−, as suggested by the overlap between the 4s electronic
states of Zn and 3p electronic states of Cl (Figure S21a, Sup-
porting Information; PDOS of Zn@C). Compared with the
hollow carbon, many newly appeared electronic states in the
TDOS of Zn@C (Figure S21b, Supporting Information; TDOS
of Zn@C and hollow carbon) also point to the strong interac-
tion between Zn and AlCl4−. The weakened interaction between
Al and Cl in Zn@C than that in hollow carbon (comparing the
PDOS of Al and Cl in Figure S21a,c) also show the Zn affects
the electronic states of AlCl4− species.[24,60–63] Another reason
contributing to the enhanced intercalation of AlCl4− in Zn@C is
the enlarged interlayer space of graphite (002) plane.[11,12,24,60–63]
Taking a three-layer graphite (002) plane as the calculation
structure, the average interlayer distance of AlCl4−-intercalated
graphite (002) in Zn@C is 6.7 Å (left side in Figure 5e), which
is larger than that (6.3 Å; right side in Figure  5e) in hollow
carbon.[24,60–63] The enlarged interlayer distance is also mani-
fested by the lower 2θ degree for the peak of graphite (002) in
the XRD patterns of Zn@C deposited on the liquid Zn cathode
than that of the carbon obtained on the solid Mo cathode
(Figure S22, Supporting Information).[11]
The low content of Zn and the powdery state makes Zn@C
not appropriate as the materials in Zn battery. The low content
of Zn in Zn@C (25 wt%; as shown in Figure S4a in the Sup-
porting Information) means the insufficient active materials for
the Zn battery. In addition, the powdery state of Zn@C implies
that substantial organic binders are needed for fabricating the
Zn@C electrode as the Zn battery, which further decrease the
content of Zn in the final Zn@C electrode.[64]
3. Conclusions
In summary, we have demonstrated a liquid zinc cathode for
accelerating electrochemical fixation of CO2 in molten salts to
advanced energy materials. Through tactfully taking advantage
of the coupling between chemical and electrochemical reactions
on the liquid Zn–molten salt interface, CO2 is successfully split
into O2 on the anode and core–shell structured Zn@C spheres
on the liquid Zn cathode. The liquid Zn serves as a depolarizer
to facilitate the reduction of CO2, and also a soft template to
direct the generation of core–shell Zn@C spheres. DFT calcu-
lations reveal that the existence of Zn enlarges the interlayer
space of graphite layer and induces strong electronic interac-
tions between AlCl4− and Zn, contributing to both enhanced
adsorption and intercalation of AlCl4− in graphitized carbon.
The core–shell Zn@C sphere hence shows enhanced aluminum
storage performance, namely, ≈90 mAh g−1 at 200  mA g−1
at the 450th cycle and negligible capacity fading after 3000 cycles
at 500  mA g−1. Implementation of affordable materials to
achieve effective carbon reduction and sustainable energy is an
imperative task. The present study provides hints on enhancing
efficiency of CO2 fixation and value-added utilization of massive
nonferrous metals in energy storage.
© 2020 Wiley-VCH GmbH
www.advancedsciencenews.com
4. Experimental Section
Molten Salt Electrolysis: Li2CO3, Na2CO3, and K2CO3 in analytical
purity were purchased from Sinopharm Chemical Regent Co., Ltd.,
China. Metallic zinc granule (99.99 wt%) was supplied by Aladdin
(Shanghai, China). All reagents were used as received without further
purification. The well-mixed salts of Li2CO3, Na2CO3, and K2CO3
(32:33:35 in weight ratio; meting point: 395  °C)  were contained in an
alumina crucible (inner diameter: 80 mm; height: 150 mm) and heated
to 450  °C.  The melted carbonate salts were used as the electrolyte.
All electrolysis was conducted with a three-electrode configuration,
consisting of the reference electrode, counter electrode, and working
electrode. Specifically, a home-made Ag/Ag2SO4 electrode was used
as the reference electrode, which was prepared as follows: 80.5  mg
of Ag2SO4 (≥99.8 wt%, Sinopharm Chemical Reagent Co., Ltd.),
852.0  mg of Li2CO3, 903.7  mg of K2CO3, and 826.2  mg of Na2CO3
were mixed well, then dried at 300  °C  for 24 h, and finally transferred
into a one-end closed corundum tube (inner diameter: 10  mm; length:
800  mm). The closed end of the tube was then heated to 850  °C  for
enabling the melting of the mixed salt, with a silver wire (≥99.9 wt%;
Wuhan Xinshenshi Chemical Technology Co., Ltd.; 2  mm in diameter)
being inserted into the bottom of the mixed salt as the current collector.
After the mixed salt was cooled to 250  °C,  argon was injected into
the tube to remove the oxygen, and the corundum nozzle was then
sealed with modified acrylate adhesive. A platinum-coated titanium
plate (Wuhan Kaida Science and Engineering Co., Ltd., China), which
is close to be inert in molten salt during electrolysis, was used as the
counter electrode (anode). Liquid Zn was used as the working electrode
(cathode). Preparation of the liquid Zn cathode was as follows: first, a
hole (≈6 cm2) on the side wall of the one-end closed aluminum tube
(inner diameter: 20 mm; length: 600 mm) was drilled to ensure the free
flow of molten salt into the alumina tube; then, Zn granules were placed
in the bottom of the alumina tube; finally, a Mo wire (2 mm in diameter)
with an alumina tube (inner diameter: 3  mm; length: 500  mm) as the
sheath was immersed into the liquid Zn and used as the electric lead.
The surface area of the liquid Zn electrode was 3.14 cm2. Without extra
mention, all the electrolysis was conducted at −0.9 V versus Ag/Ag2SO4
and 450 °C for 3 h, with an CO2 flow (100 mL min−1) being injected into
the electrolysis cell for enabling the capture of CO2 by O2− in molten
salts during the whole process. CV curves were also recorded using
the above-mentioned three-electrode configurations at 5  mV s−1 on an
electrochemical workstation (CHI 1140E, CH Instruments Inc., Shanghai,
China). For comparison, the liquid Zn working electrode was replaced
by a solid Mo wire (2 mm in diameter) in one case for acquiring the CV
curves at 5  mV s−1 or obtaining the carbon on the solid Mo electrode.
After electrolysis, the obtained Zn@C samples in the cathode were
collected and washed with 1 m HCl solution for 10 h and deionized water
for several times to remove the frozen electrolyte, and finally dried at
70  °C  overnight. For comparison, hollow carbon shell was obtained by
etching Zn@C in concentrated HCl solution (2.5 m) for 10 h to remove
the Zn core. Also, the Zn core was partially removed by leaching the
Zn@C in the 2.5 m HCl solution for a short period (2 h). In one case,
the liquid Zn was soaked in the 450  °C  Li2CO3–Na2CO3–K2CO3 molten
salt for 3 h without electrolysis to understand the chemical reactions
between Zn with the molten salts. The current efficiency (η, %) and
energy consumption (EC, kWh kgC−1) were calculated by the following
equations[8]
mC
4× ×F
4 × nC × F MC (1)
η= =
Q Total ∫ idt
U ∫ idt
EC =
mC (2)
where nC (mol) and mC (g) are the molar amount and the mass of
obtained carbon, respectively, MC (12  g mol−1) is the molar mass of
carbon, F (96  485 C mol−1) is the Faraday’s constant, QTotal (C) is the
total charge passed during the electrolysis, i (A) is the electrolysis
Adv. Energy Mater. 2020, 2002241 2002241  (9 of 11)
www.advenergymat.de
current, and t (s) is the time. U (V) is the voltage difference between
the working electrode and the counter electrode, which is monitored by
a separate electrochemical working station (CHI 660E, CH Instruments
Inc., Shanghai, China), as shown in Figure S23 in the Supporting
Information.
Characterization: The morphologies of the obtained products on
the cathode were characterized through FESEM (Zeiss SIGMA) and
TEM (TecnaiG2F30/F20, FEI, America) equipped with the elemental
mapping images. XRD was carried out on Rigaku Miniflex600 with
a Cu Kα source at a wavelength of 0.154  nm. XPS was performed on
ESCALAB250Xi (Thermo Fisher Scientific, America), whose C 1s as a
reference signal was adjusted to 284.8 eV. Raman spectra was recorded
on a Raman microscope (Renishaw in Via). The specific surface area
and pore size distribution were measured on the micromeritics TriStarII
and determined by Brunauer–Emmett–Teller (BET) and Barrett–Joyner–
Halenda (BJH) methods. Thermogravimetric analysis (TGA, Mettler
Toledo DSC1) was performed in air at a heating rate of 10 °C min−1 from
room temperature to 850 °C.
Electrochemical  Tests  of Al-Ion Batteries: The obtained products
were employed as the positive electrode materials in AIBs, in which
aluminum worked as the negative electrode. The products were mixed
homogeneously with acetylene black and polyvinylidene fluoride (PVDF)
by a weight ratio of 7:2:1 in N-methyl-2-pyrrolidone (NMP). Then, the
slurry was pasted on a tantalum (Ta) foil current collector, and then dried
in air oven at 60  °C  for 6 h. The AlCl3 and 1-ethyl-3-methylimidazalium
chloride ([EMIm]Cl) were mixed in a molar ratio of 1.3:1 as the electrolyte.
Using a glass membrane as the separator, the CV measurements were
conducted on CHI 660E (Shanghai, China) at a scan speed of 0.5 mV s−1
from 0.3 to 2.3 V versus Al/AlCl4−. The Neware BTS-53 tester was applied
to test the charge/discharge performance of the batteries at current
densities of 200 and 500 mA g−1 in the potential range between 0.3 and
2.3 V (vs Al/AlCl4−) at room temperature. For comparison, the commercial
metallic Zn powder (analytical reagent, provided by Sinopharm Chemical
Reagent Co., Ltd.) as the electrode material was also tested, with the
same procedures being used for fabricating the electrodes.
DFT Calculations: The DFT calculations were performed by using
Vienna Abinitio Simulation Package (VASP) with projector augmented
wave (PAW) method.[65–68] Perdew–Burke–Ernzerhof (PBE) functional for
the exchange–correlation term was used with the projector augmented
wave method,[69,70] with the kinetic energy cutoff of electron wave
functions being set as 450  eV. The convergence of energy and forces
were set to be 1 × 10−6  eV and 0.015  eV Å−1, respectively. The van der
Waals interactions play a very crucial role for the layered systems,
therefore the DFT-D3 approach was used for the correction of van der
Waals interactions that adds the vdW correction for potential energy
and interatomic forces.[71] The (002) crystal plane of graphite was used
for constructing the layered structure of graphite. A Zn7 nanocluster
containing seven zinc atoms was placed on the surface or inside the
interlayer space of graphite (002) to probe the effect of Zn for adsorption
or intercalation of AlCl4− in sample Zn@C. Correspondingly, Zn-free
graphite (002) was also considered to understand the adsorption or
intercalation of AlCl4− in the hollow carbon shell, which is denoted as
hollow carbon. For the adsorption of AlCl4− on the graphite (002) slab, a
AlCl4− monomer was placed on the upper surface of a two-layer-graphite
(002) slab. For intercalation of AlCl4− on the graphite (002) slab, a three-
layer-graphite (002) layer was constructed and the AlCl4− monomer was
placed inside the interlayer space.[60–62] After structure optimizations,
the adsorption (Eads) and intercalation (Eint) energies of AlCl4− on the
graphite (002) were then calculated by the following equations[72]
E ads = E slab
ads − E ads − E
slab (3)
E int = E slab
int − E int − E
slab (4)
ads and E int are the calculated energies of AlCl −-adsorbed slab
where E slab slab 4
and AlCl4−-intercalated slab, respectively. Eads and Eint are the energy of
−
adsorbates or intercalation species, namely, AlCl4 herein, in gas phase.
Eslab is the energy of pure slabs.
© 2020 Wiley-VCH GmbH
www.advancedsciencenews.com
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors acknowledge the funding support from the National
Natural Science Foundation of China (51722404, 51674177, 51804221, and
91845113), the National Key R&D Program of China (2018YFE0201703),
the China Postdoctoral Science Foundation (2018M642906 and
2019T120684), the Fundamental Research Funds for the Central
Universities (2042017kf0200), the Hubei Provincial Natural Science
Foundation of China (2019CFA065), and the High-level Talent Project of
Hainan Natural Science Foundation (2019RC075).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
CO2 fixation, core–shell structures, energy storage, liquid zinc, molten
salt electrochemistry
Received: July 9, 2020
Revised: August 20, 2020
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