Chinese Chemical Letters 34 (2023) 108143

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Chinese Chemical Letters

journal homepage: www.elsevier.com/locate/cclet

Fan-like MnV2 O6 superstructure for rechargeable aqueous zinc ion

batteries
Shixian Wang a , Yue Ru b , Yangyang Sun a , Huan Pang a,∗
a
School of Chemistry and Chemical Engineering, and Institute for Innovative Materials and Energy, Yangzhou University, Yangzhou 225009, China
b
Interdisciplinary Materials Research Center, Institute for Advanced Study, Chengdu University, Chengdu 610106, China

a r t i c l e i n f o a b s t r a c t

Article history: In recent years, vanadate has attracted the attention of researchers for its application in electrode mate-
Received 12 November 2022 rials due to its high specific capacity and layered crystal structure. Herein, a typical manganese vanadium
Revised 21 December 2022
oxides (MnV2 O6 ) product is efficient synthesis via a simple one-step hydrothermal method at 200 °C for
Accepted 10 January 2023
16 h. The as-prepared MnV2 O6 sample is found to be the unique one-dimensional fan-like superstructure
Available online 13 January 2023
consist of several nanorods. From a microcosmic point of view, VO6 octahedra sheets are connected by
Keywords: sharing edges which provides highly-open framework for rapid the intercalation and deintercalation of
One-dimensional MnV2 O6 guest ions Therefore, stable MnV2 O6 was prepared and used as a cathode material in aqueous zinc ion
Fan-nanorod superstructure batteries, which displayed favorable specific discharge capacity, excellent coulombic efficiency and well
Aqueous Zn-ion batteries cycling performance.
Energy storage © 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia
Cathode material
Medica, Chinese Academy of Medical Sciences.

Given the growing concern over rapidly diminishing traditional In recent years, research has focused on one-dimensional (1D)
fuel reserves and the serious environmental problems, sustainable or quasi-1D nanostructures, such as nanowires, nanotubes and
energy resources such as solar and wind have come under global nanoribbons, whose shapes provide them unique physical and
spotlight, which triggering the search for reliable, safe and eco- chemical properties that greatly broaden their potential in energy
nomical electrochemical energy storage and conversion technolo- storage devices [19]. Compared to other structures the 1D nanos-
gies [1–5]. In this case, the development of energy storage systems tructure has a larger specific surface area and faster ion diffu-
is essential for providing more functional and stable energy sup- sion rate. This is very beneficial for its capacity, rate capacity and
ply, and it is necessary to seek energy storage devices with strong long-term cycling stability as electrode materials. However, a well-
adaptability and high efficiency [6–8]. The potential application of arranged array is more conducive to improving the stability of
waterborne zinc ion batteries (ZIBs) in large-scale energy storage 1D nanomaterials in application to accentuate the anisotropy and
devices has been widely recognized. Owing to its the theoreti- conforms to the equipment design scheme. Among them, man-
cal capacity, relatively low redox potential and stability in water ganese vanadium oxides (MnV2 O6 ) with brannerite structure as
due to a high overpotential for hydrogen evolution [9–13]. In re- classic representative of AB2 O6 compounds (A = Co, Mn, Mg, Zn,
cent years, as different aqueous ZIBs cathode materials have been Cu, and B = V+5 ) have received a great attention as an emerg-
studied and attempts have been made to improve them. How- ing electrode material due to their structural relationship with
ever, certain problems cannot be ignored, such as unstable layered γ -MnO2 and nonstoichiometric manganese dioxide for the bat-
structure and low electronic conductivity, which lead to poor cy- tery industry [20–22]. The MnV2 O6 compounds have been classi-
cle capacity and stability. To solve these issues, many optimization fied as monoclinic structure with a C2/m space group. It consists
strategies have been developed, such as adjusted pH to influence of VO6 octahedral chains interconnected to form two parallel an-
dendrite formation and constructed inorganic interface to suppress ion sheets, and Mn2+ are located between the oxygen sheets. In
water decomposition etc. [14–16]. However, it still faces numerous the event of chemical oxidation/reduction, the two metals can act
challenges of serious capacity degradation and inferior rate capa- as buffer substrates for each other, maintaining structural stabil-
bility [17,18]. Therefore, it is urgent to research into efficient aque- ity more effectively, which is suitable for Zn2+ insertion or extrac-
ous ZIB cathode materials. tion [23]. Recently, the successful synthesis of crystalline MnV2 O6
compounds has been reported, such as solid-state reaction [24],
∗
co-precipitation [25], polymer gelation [26] and autogenous hy-
Corresponding author.
drothermal methods [27]. Several experiments have demonstrated
E-mail address: huanpangchem@hotmail.com (H. Pang).

https://doi.org/10.1016/j.cclet.2023.108143
1001-8417/© 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
S. Wang, Y. Ru, Y. Sun et al. Chinese Chemical Letters 34 (2023) 108143

Fig. 1. The MVO-16 sample structural characterization of the as-obtained nanorods:

(a-d) SEM images of different magnification; (e, f) TEM images under different mag-
nification; (g) HRTEM image; (h) SAED pattern; (i) EDS elemental mapping images.

that the MnV2 O6 morphology in relation to electrochemical prop-

erties is strongly influenced by the synthesis and processing meth-
ods. Often these methods are complex and require demanding re-
action conditions, which leaves the product without morphological
control. The hydrothermal method is considered superior to the
above methods because it requires no additional heat treatment
to obtain a pure crystalline phase and takes less time and effort.
For instance, Huang et al. [19] prepared MnV2 O6 nanobelts via hy-
drothermal route and utilized for lithium-ion batteries, which still
maintain excellent cycling stability and reversible capacity under
high current density. Fig. 2. (a) XRD pattern of MVO-16 sample. (b) FTIR spectrum of the as-prepared
MnV2 O6 samples for 8–72 h. (c) The schematic crystalline structure of the MnV2 O6
Herein, we have synthesized MnV2 O6 products by a facile one-
unit cell from different axes. XPS spectra of the MVO-16: (d) Survey scan, (e) Mn2p
pot hydrothermal method at a temperature of 200 °C for different and (f) V2p .
durations. A series of 1D MnV2 O6 are arranged together by self-
arrangement to form a fan, and the interior is arranged in layers,
which providing an open and flexible channel for the rapid inser-
tion of guest ions. The electrochemical performance was investi- image of differernt magnification (Figs. 1e and f). The TEM im-
gated by fabricating a cost-effective MnV2 O6 //Zn battery utilizing ages demostrate the uniform arrrayed nanorods exhibit the solid
MnV2 O6 samples as the cathode material in 3 mol/L Zn(CF3 SO3 )2 struture with a width of ≈400 nm for every nanorod on average.
electrolyte. Owing to the unique 1D fan-like superstructure, the To gain further insight into the atomic-scale structure, a high-
battery exhibited favorable specific discharge capacity, excellent resolution TEM (HRTEM) is illustrated in Fig. 1g. The HRTEM fig-
coulombic efficiency and well cycling performance. This work pro- ures of MVO-16 can be clearly seen, showing good crystallinity.The
vides new insights for improving the storage capacity of Zn2+ for inter-planar space was measured to be 0.33 nm, which is corre-
practical applications. sponded to the (110) plane of MnV2 O6 [29]. The fact that the
A series of MnV2 O6 products were prepared by a hydrothermal nanobelts are single crystal is confirmed by the (110) plane of
method at 200 °C for different hydrothermal durations from 8 h to MnV2 O6 parallel to the growth direction of the nanorods. At the
72 h. The products were named as MVO-X (X represent hydrother- same time, the selected area electron diffraction (SAED) diagram
mal durations, X = 8, 16, 32, 48, 72). The morphology of MnV2 O6 of a single nanorod was carried out (Fig. 1h), which proved the tip
samples obtained from scanning electron microscopy (SEM) at dif- diffraction characteristics of MnV2 O6 single crystal were consistent
ferent magnifications, as shown in Figs. 1a-d and Fig. S1 (Sup- with the X-ray diffraction (XRD) results [21]. The elemental com-
porting information) [28]. When the reaction condition is from position of MnV2 O6 was further to analyze by energy dispersive
8 h to 48 h, most of as-prepared the MnV2 O6 samples demonstrate X-ray spectroscopy (EDS) elemental mapping. As shown in Fig. 1i,
the 1D fan-like arrangements of morphology. A series of nanorods elements Mn, V and O are uniformly distributed throughout the
with irregular shape sizes are arrayed together to form the fan- fan-like structure.
like shapes through self-arrangement. Especially, MVO-16 samples Fig. 2a shows the XRD patterns of all MnV2 O6 samples for dif-
have the most uniform size and morphology, indicating that the ferent hydrothermal durations to qualitatively analyze the phase
appropriate reaction time may have a certain influence on the ho- constitution. The diffraction patterns show several characteristic
mogeneous morphology of the synthesized substance. In addition, diffraction peaks, which are well matched with the standard data
it can also be observed in Figs. S1g and h that when the reaction (ICSD #40,850), indicating that crystalline all MnV2 O6 products
time was increased to 72 h, those nanorods bound together before were successfully synthesized by the hydrothermal method. From
dispersed and gradually turned to form as slender nanowires. Such the comparison to the standard data, there is no more peaks from
phenomenon may be resulted from relatively longer reaction time. other phases have been detected in the samples, which are per-
Morphology and microstructure of the as-prepared MVO-16 was fectly refracted into pure monoclinic phase with the space group
further explored by the transmission electron microscopy (TEM) of C2/m (No. 12) and lattice constants of a = 9.3287 Å, b = 3.536 Å,

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S. Wang, Y. Ru, Y. Sun et al. Chinese Chemical Letters 34 (2023) 108143

c = 6.765 Å and β = 112.29° [30,31]. It can be seen that the intensity

of the (−202) peak was relatively strong in both samples, which
means that preferential orientation makes the microcrystals have
special shapes. With the extension of reaction time, the diffrac-
tion reflection intensity also increases, which indicates that the
crystallinity of the samples was improved. Among them, it can be
seen that the diffraction intensity of MVO-16 is relatively stronger
compared to other samples, manifesting that the MnV2 O6 sample
reacted for 16 h possesses the better phase purity and crystallo-
graphic structure. From the crystal structure diagram, the inter-
nal structure of MnV2 O6 can be more clearly understood (Fig. 2c).
The interior of MnV2 O6 structure is composed of layered struc-
tures, and each layer structure is connected by a 1D octahedral
MnO6 chain and a tetrahedral VO4 chain. It is worth noting that
these two kinds of 1D chains, each of which is extended in the
form of octahedron and tetrahedron edges and corners, are linked
to each other. The bond distance between Mn1-O1 and Mn1-O2
in MnO6 chain is the same and symmetrical. On the contrary, the
VO6 complex is equipped with asymmetrical shape [25]. In fact,
the distance of these V-O bonds are different. According to them,
it is shown that the smallest V1-O2 bond is equal to 1.66 Å, while Fig. 3. Cyclic voltammetry of the MVO-16 cathode in aqueous Zn(CF3 SO3 )2 elec-
trolyte: (a) Initial three cycles of CV curves at 0.1 mV/s; (b) Typical CV curve at dif-
largest one is equal to −2.52 Å. This special V coordination can
ferent scan rates of 0.1–1 mV/s; (c) log(i) versus log(v) plots at the cathodic current
provide more possibilities for anisotropic growth, which is aligned response at four peaks; (d) Separation of the capacitive and diffusion-controlled
or oriented [32]. As shown in Fig. 2b, the samples were further charge contributions ratios at different scan rates.
characterized by Fourier transform infrared spectroscopy (FTIR),
and the wave number range was 80–40 0 0 cm−1 . The band at 547
cm−1 is due to v(V-O-V) symmetric and asymmetric stretching vi- host framework. It is worth noting that the broad peaks on CV
bration of polymeric metavanadate [33]. The absorption band ob- curves and pseudo linear voltage responses on galvanostatic charge
served at 892 cm−1 can be ascribed to the short V-O bonds (1.665 and discharge (GCD) curves (Figs. 4a-d) mean the intercalation
and 1.679 Å) in MnV2 O6 while the peak located at 795 cm−1 is pseudocapacitive behavior of Zn2+ . In Fig. S4 (Supporting informa-
assigned to the V-O bonds of 1.86 Å. The weak absorption peak tion), the CV measurement of MVO-X (X = 8, 32, 48, 72) electrodes
located at 1624 cm−1 and the flat shoulder band at 3433 cm−1 are also carried out and the shapes are mostly similar to MVO-16
may be corresponded to the bending and stretching vibrations of with a little difference. The CV curve (Fig. 3b) at different sweep
absorbed H2 O or hydroxyls. Based on the characterization results velocities from 0.1 mV/s to 1 mV/s can more intuitively reflect the
mentioned above, it can be concluded that the MVO-16 sample has electrochemical reaction kinetics of MVO-16. With the increasing
achieved more homogeneous morphology better crystalline struc- scan rate, the CV curves maintain the original curve shape and the
ture, which as it were verifies 16 h to be the better hydrothermal position of the redox peaks, but there are still some slight devia-
reaction condition. tions. These cyclic curves are highly coincident, indicating that the
To qualitatively evaluate the chemical compositions, the ele- reversibility and stability of the intercalation/deintercalation pro-
ment valence states and surface energy state distribution of the cess of Zn2+ in the Zn//MnV2 O6 batteries. In addition, the pairs of
compounds, X-ray photoelectron spectroscopy (XPS) test of the obvious reduction and oxidation peaks can be observed, indicating
MnV2 O6 samples are conducted and the results are separately that a two-step intercalation/deintercalation process of Zn2+ dur-
shown in Figs. 2d–f, Figs. S2 and S3 (Supporting information) [28]. ing cycling. The two cathode peaks possible represent that inter-
To take the MVO-16 sample as an example in Fig. 2d, we found the calation of Zn2+ into the V-O network and the reduction of MnO
presence of Mn, V, and O elements in the samples, which can be to Mn [38,39]. XPS characterization results showed the presence of
further supported by EDS mapping. V4+ and Mn2+ , the specific reaction equation will be introduced
XPS spectrum of Mn element, the binding energy at 641.6 eV in the next section. The anode peak is due to the reconversion of
corresponds to Mn 2p3/2 and the binding energy at 653.6 eV cor- metallic Mn and the detachment of Zn2+ from the host framework
responds to Mn 2p1/2 (Fig. 2e) [34]. This indicates that Mn exists [23].
in the form of divalent metal cations. Besides, two peaks presented Besides, CV curves of MVO-X (X = 8, 32, 48, 72) at different
in Mn3s region in the range around 82.9–89.2 eV with peak separa- scan rates of 0.1–1.0 mV/s were obtained in Figs. S4e-h. It can be
tion of 6.2 eV in Fig. S2a, further revealing the existence of Mn2+ as observed that all shapes of the curves of the CV are almost un-
well. In the V2p XPS spectrum (Fig. 2f), there are two obvious peaks changed, demonstrating the excellent reversibility of the electro-
at the 516.7 and 524.8 eV binding energies, respectively which are chemical reactions for the MnV2 O6 electrode. With the increase of
correspond to V 2p3/2 and V 2p1/2 [35]. Besides, the main peak scanning rate, the polarization increased due to the kinetic limita-
at 530 eV can be ascribed to V-O stretch bond (Fig. S2b). The XPS tion of Zn2+ diffusion in Zn-V-O matrix, resulting in the increase of
analysis of other MnV2 O6 samples MVO-X (X = 8, 32, 48, 72) shows peak current gap between cathode and anode scanning. According
the similar result to the MVO-16 sample in Fig. S3. to previous studies, the insertion and extraction mechanisms can
To evaluate the electrochemical performance, the coin cell-type be expressed by the following formulas [23]:
batteries are assembled using zinc metal foil as anode, the MnV2 O6 At the irreversible initial discharge process:
samples as cathode material in 3 mol/L Zn(CF3 SO3 )2 solution as
electrolyte at a voltage range of 0.4–1.4 V [36,37]. As shown in Fig. MnV2 O6 + xZn2+ + 2xe− → Mn + Znx MnV2 O6 + ZnO (1)
3a, when the scanning rate is 0.1 mV/s, the cyclic voltammetry (CV)
curves of MVO-16 for the first three cycles, which indicates that Reversible charge/discharge process:
the redox reaction occurs when Zn2+ charge/discharge from the
Mn + ZnO ↔ MnO + Zn2+ + 2e− (2)

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S. Wang, Y. Ru, Y. Sun et al. Chinese Chemical Letters 34 (2023) 108143

Fig. 4. (a-d) Galvanostatic charge/discharge profile of MVO-16 for different cycles at different discharge current densities of 20, 30, 50 and 100 mA/g; (e-h) Cycling perfor-
mance at different discharge current densities of 20, 30, 50 and 100 mA/g.

Intercalation/deintercalation reaction: the range of 0.6–0.9, which also indicates these two forms of con-
tribution to controll the electrochemical reaction by coordination
Znx MnV2 O6 ↔ Znx-y MnV2 O6 + yZn2+ + ye− (3) [42]. The pseudocapacitance contribution rate of the intercalation
can be calculated by the following formula [43,44]:
According to previous, the electrochemical mechanism of VO2
i = k1 v + k2 v1/2 (8)
in MnV2 O6 //Zn batteries is proposed [40,41]:
Anode:
i/v1/2 = k1 v1/2 + k2 (9)
xZn ↔ xZn2+ + 2xe− (4)
where k1 v and k2 v1/2 respectively represent the contribution of ca-
Cathode: pacitance and diffusion control to the total current. Combined with
the formula, it is easy to fit the contribution of its capacitive cur-
xZn2+ + VO2 + 2xe− ↔ Znx VO2 (5) rent (k1 v) to the total current at different scanning rates. As shown
in Fig. 3d, the contributions from pseudocapacitive reactions are
Kinetics analysis is carried out to further explore the electro- 45.3%, 53.9%, 58.9%, 62.3% and 64.9% as the increasing the sweep
chemical performance of the MVO-16 electrode and the CV curve rate from 0.1 mV/s to 1.0 mV/s. This result indicates that the bat-
at 0.1–1 mV/s is investigated in Fig. 3c. The relationship between tery is mainly controlled by ionic diffusion and pseudocapacitance
the current i (mA) with the scan rate v (mV/s) is as follows: synchronously. The electrochemical process is mainly dominated
by pseudocapacitive behavior at high scan rates, which is bene-
i = avb (6) ficial for delivering excellent electrochemical properties [45]. Ac-
cordingly, as is depicted in Figs. S5e-h (Supporting information),
 the capacitive contributions of MVO-X (X = 8, 48, 72) at various
log i = b log(v ) + log(a ) (7)
scan rates are obtained to be in the range of about 32%∼58% except
where a and b are constants obtained by fitting straight lines. If the MVO-32, which as well manifests the control of capacitive and dif-
b = 0.5, the electrochemical reaction generally indicates a diffusion- fusion synergistically during the reaction. Compared the capacitive
controlled intercalation, while b = 1.0 the electrochemical reaction contributions of MVO-16 to other samples obtained for other time,
suggests that the reaction is surface-limited. there is a little superiority of capacitive control for MVO-16, which
According to the equation, log(i) vs. log(v) curves for sweep may be beneficial to the fast ionic migration and demonstrating
rates ranging from 0.1 mV/s to 1 mV/s can be plotted respectively, better electrochemical performance [46].
from which four redox peak b values are 0.88, 0.60, 0.89 and 0.67. The GCD was used to characterize the electrochemical perfor-
According to the b value, the charge/discharge process is controlled mance of as-prepared MnV2 O6 [47]. The GCD curves of MVO-16
by both ion diffusion and surface controlled reaction synergisti- sample for 1st , 2nd , 3rd ,10th , 20th and 50th cycles at 20 mA/g were
cally.The specific b values of other sapmles for different durations first performed in Fig. 4a [48]. Obviously, two discharge voltage
in Figs. S5a-d (Supporting information) were calcualted fitting in plateaus appear in 0.9 V and 0.65 V. which corresponds to the re-

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S. Wang, Y. Ru, Y. Sun et al. Chinese Chemical Letters 34 (2023) 108143

sult of CV curve [49]. Compared with the first cycle, discharge ca- relative large impedance should still be a problem affects the bat-
pacity decreases markedly from the second cycle, but both dis- tery performance. Therefore, to further reduce the impedance the
charge and charge capacities decrease gradually afterwards and Zn//MnV2 O6 battery in the future research is still neccessary to be
the charge capacity became even close to the discharge capacity improved.
[50,51]. To investigate the rate properties, the GCD curves at dif- In conclusion, we successfully fabricated the 1D MnV2 O6
ferent scan rates from 20 mA/g, 30 mA/g, 50 mA/g and 100 mA/g nanorods via a facile hydrothermal reaction at a temperature of
are also conducted in Figs. 4a-d. With the charge/discharge cur- 200 °C for different duration and obtained MnV2 O6 nanorods
rent density increases, the initial discharge capacity of MVO-16 de- with uniform fan-like superstructure for 16 h. These products were
creases from 30, 27.5, 25 mAh/g to 13.5 mAh/g. This phenomenon used as the cathode material for aqueous MnV2 O6 //Zn batter-
might be due to the intrinsic characteristics of MnV2 O6 products ies in 3 mol/L Zn(CF3 SO3 )2 solution at a voltage range of 0.4–
with 1D nanorods structure, which reduced the diffusion distance 1.4 V. The MnV2 O6 structure is arranged in layer network while
of Zn2+ and electrons in the solid state [19]. Different discharge each layer consists of octahedral MnO6 chains and tetrahedral
capacities of 24.2, 20.1 and 19.6 mAh/g were achieved MOV-16 an- VO4 chains, which provides open and flexible channels for Zn2+
ode after 2, 20 and 50 cycles at 20 mA/g, respectively. At the same transfer. Taken advantage of such superstructure, the assembled
time, with the increase of the cycles number, the discharge capac- MnV2 O6 //Zn battery exhibited favorable specific discharge capac-
ity of the MOV-16 decays slowly, indicated that MOV-16 had well ity, excellent coulombic efficiency, and well cycling performance.
cycling performance. Based on this, the GCD properties of MVO- Therefore, this investigation proved the metal vanadate material
X (X = 8, 32, 48, 72) are measured at for 1st , 2nd , 3rd ,10th , 20th has great potential for ZIBs. Since the electrochemical performance
and 50th cycles at different current densities in Figs. S6a-d, S7a-d, of vanadate is highly dependent on interlayer cations, doping or
S8a-d and S9a-d (Supporting information). The initial discharge ca- substituting cations is a promising strategy to further improve the
pacities are displayed to be 40, 45, 58 and 18 mAh/g, respectively, electrochemical performance of ZIBs. This study provides a new
which indicates that the discharge capacities of MnV2 O6 //Zn bat- choice in the future for high-performance electrodes and has great
teries will become better the with the increase of the hydrother- potential for building the next generation energy storage devices.
mal time. However, the decrease of discharge capacity of the MVO-
72 may be result from the inherent influence of different material Declaration of competing interest
morphologies.
To further examine the cycling stability of MnV2 O6 products, The authors declare that they have no known competing finan-
the cyclic performance of MVO-16 at different current densities are cial interests or personal relationships that could have appeared to
depicted in Figs. 4e-h. As shown in Fig. 4e, the battery remained influence the work reported in this paper.
the 51.4% retention of initial discharge capacity after 140 cycles and
the coulombic efficiency is nearly 100% throughout the whole cy-
Acknowledgments
cling process. As the current density raised up, the capacity degra-
dation accordingly came to be larger, which is displayed in Figs.
This work was supported by the National Natural Science Foun-
4f-h. Compared to MVO-16, the cycling performance of other sam-
dation of China (No. U1904215), the Natural Science Foundation of
ples in Figs. S6e-h, S7e-h, S8e-h and S9e-h (Supporting informa-
Jiangsu Province (No. BK2020 0 044), and the Changjiang Scholars
tion) displays poorer charge/discharge reversibility and long lifes-
Program of the Ministry of Education (No. Q2018270).
pan than MVO-16 which may be because of the less stable struc-
ture framework and slower ionic diffusion. However, these samples
still exhibit excellent coulombic efficiency reaching almost 100%. Supplementary materials
These results indicate that the redox reaction still occurs when an
irreversible transformation of the crystal structure does not gener- Supplementary material associated with this article can be
ate [44]. found, in the online version, at doi:10.1016/j.cclet.2023.108143.
In order to elucidate the resistance change of MVO-16 during
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