Nanotechnology

ACCEPTED MANUSCRIPT

Three-dimensional BiVO4-based semiconductor photocathode for high

efficiency photo-assisted Zn-iodine redox flow batteries
To cite this article before publication: Maolin Dong et al 2022 Nanotechnology in press https://doi.org/10.1088/1361-6528/ac5f83

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Page 1 of 11 AUTHOR SUBMITTED MANUSCRIPT - NANO-131905.R1

IOP Publishing Journal Title

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Three-dimensional BiVO4-based semiconductor

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10 photocathode for high efficiency photo-assisted
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Zn-iodine redox flow batteries

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16 Maolin Dong1, Yijie Wang1, Aoshuang Li1, Chuanwei Cheng1*
17 1 Shanghai Key Laboratory of Special Artificial Microstructure Materials and Technology, School of
18 Physics Science and Engineering, Tongji University, Shanghai 200092, P. R. China
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20 E-mail: cwcheng@tongji.edu.cn

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22 Received xxxxxx
23 Accepted for publication xxxxxx
24 Published xxxxxx
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26 Abstract
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an
Aqueous Zn-iodine redox flow batteries have aroused great interest for the features of high
capacity, excellent stability, low cost, and high safety, yet the dissatisfying energy efficiency
still limits their future advancement. In this work, three-dimensional semiconductor BiVO4
30 nanoparticles decorated hierarchical TiO2/SnO2 arrays (BiVO4@TiO2/SnO2) were applied as
31 photocathode in Zn-iodine redox flow batteries (ZIRFBs) for the realization of efficient
32
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photo-assisted charge/discharge process. The photogenerated carriers at the solid/liquid
33
interfaces boosted the oxidation process of I-, and thus contributed to a significant elevation in
34
energy efficiency of 14.9% (@0.5 mA cm-2). A volumetric discharge capacity was extended
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by 79.6% under light illumination, owing to a reduced polarization. The photocathode also
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exhibited an excellent durability, leading to a stable operation for over 80 h with a maintained
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high energy efficiency of ~90% @0.2 mA cm-2. The research offers a feasible approach for
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39 the realization of high-energy-efficiency aqueous Zn-iodine batteries towards high-efficiency
40 energy conversion and utilization.
41
42 Keywords: Zn-iodine redox flow batteries, photoelectrode, energy efficiency.
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50 pioneers towards the construction of large-scale energy
51 1. Introduction
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storage and conversion systems due to their high energy

52 density.[5] However, the high cost of lithium metal and the
The ever-growing energy demand raises new challenges
53 potential safety risks hinder the further advances of lithium-
on efficient energy conversion and utilization.[1] Up to date,
54 ion batteries.[6] As a strong competitor, Zn-based redox flow
electrochemical energy storage systems have occupied a
55 batteries exhibit attractive advantages, including low cost and
significant status in real-life applications, for turning the
56 high earth abundance of zinc metal, environmental
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57 intermittent renewable power sources into stable chemical

friendliness and high safety of aqueous electrolyte, high
58 energy, and then supplying time/weather dependent-free
chemical reversibility of halogen-based redox couples, and
59 continuous electrical power supply when needed.[2-4] Under
long-time stability, and high capacity of the electrolyte flow
60 this circumstance, lithium-ion batteries are one of the
feature.[7-12] Zn-iodine redox flow batteries (ZIRFBs), as a

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 AUTHOR SUBMITTED MANUSCRIPT - NANO-131905.R1 Page 2 of 11

Journal XX (XXXX) XXXXXX Author et al

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3 typical system, operate on the basis of Zn/Zn(OH)42- and
4 highly soluble I3-/I- redox couples, yet ZIRFBs still suffer
5 from the sluggish reaction kinetics in the oxidation from I- to
6 I3-, in the charge process, which directly lead to high charge
7 potential and low energy efficiency of the devices. [13, 14]
8 In this regard, the construction of semiconductor
recipes were adopted our previous reports.[26, 27] First,
monolayered polystyrene microsphere arrays were assembled
on FTO substrate via a self-assembly method. Second, a
SnO2 layer with an average thickness of 14 nm was deposited
by atomic layer deposition (ALD) as a seed layer. Then, the
SnO2 nanosheets were uniformly grown on the SnO2 sphere

9 photoelectrodes to utilize solar energy for boosting the
10 oxidation kinetics is a powerful method of realizing
11 simultaneous conversion and storage of solar energy, so as to
12
assist charging and improve energy efficiencies in
13
batteries.[15, 16] The photo-induced promotion is applicable in
pt
arrays through a hydrothermal method and the following
annealing under air. Consequently, a TiO2 layer with a
thickness of 5 nm was deposited on SnO2 nanosheets by
ALD. Finally, BiVO4 nanoparticles was electrochemically
deposited on the surface of TiO2/SnO2 arrays so that

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14
multiple electrochemical energy conversion systems, such as BiVO4@TiO2/SnO2 was acquired. The details in synthesis
15
Zn-air batteries,[12, 17] Lithium-iodine batteries,[18] and Li-O2 are described in Supplementary Materials.
16
batteries,[19-21] with various semiconductor materials, e.g.
17
TiO2,[22, 23] Fe2O3,[15, 18] WO3.[24, 25] Under solar illumination, 2.2 Characterizations
18
19 the photo-excited holes in semiconductors can promote the
The morphology and microstructure of
20 oxidation reaction at the cathode, while the corresponding
BiVO4@TiO2/SnO2 was observed by FEI Sirion 200 field

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21 electrons are transported to the external circuit, further
emission scanning electron microscope and FEI TALOS
22 participating in the reduction at the anode.[13] By this means,
F200X transmission electron microscope, and the crystal
23 the charge potential can be significantly lowered and thereby
structure and phase composition were determined by X-ray
24 a higher overall energy efficiency of the battery devices can
diffraction spectormeter (D8-Advance, Bruker Miller). The
25 be achieved. Therefore, introducing semiconductor
chemical state analysis was collected by X-ray photoelectron
26 photoelectrodes into ZIRFBs is a feasible approach to tackle
27
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29
the charge issues and optimize the battery performance.
Herein, we fabricated three-dimensional hierarchical
BiVO4@TiO2/SnO2 arrays on FTO substrate, and directly
an spectrometer (Thermo Kalpha). Ultraviolet photoelectron
spectroscopy (UPS) profiles obtained on ultraviolet
photoelectron spectrometer (Thermo EscaLab 250Xi), and
the transmittance measured on UV-vis spectrophotometer
30 applied in the ZIRFBs as cathodes with a photo-assisted
(Hitachi, U3900H), were deployed for the determination of
31 charge feature. In this ternary BiVO4@TiO2/SnO2 composite
energy band profiles of materials.
32 photocathode design, the SnO2 hierarchical nanosheets act as
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33 3D conductive skeletons, BiVO4 nanoparticles work as light 2.3 Assembly of Zn-iodine redox flow batteries
34 absorbers, and TiO2 as medium layer to facilitate the charge
35 transfer process. The three-dimensional hierarchical structure Homemade battery modules were used for the assembly
36 ensures that the key active material, BiVO4 nanoparticles, and fixation of the whole devices. The BiVO4@TiO2/SnO2
37 can be in full contact with the electrolyte and efficiently on FTO was directly applied as the cathode, and the
38 participated in the oxidation reaction of iodide ions. corresponding electrolyte was 4 M KI-4 M I2. Pre-polished
39 Furthermore, the rational construction of ternary zinc foil was used as the anode, and the corresponding
40 semiconductor heterojunction facilitates the rapid oriented electrolyte was 4 M KOH with 0.2 M zinc acetate (ZnAc2).
41 transportation of photo-excited carriers. As a result, the The exposed area for each electrode to the corresponding
42 electrolyte was 1 cm2. The separator was selected to be a
BiVO4@TiO2/SnO2-based ZIRFBs achieved an enhancement
43
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of 14.9% in energy efficiency, and an extended discharge pretreated Nafion 117 cation exchange membrane. The
44 pretreatment process is that, the purchased membrane was
capacity of 85.5 mAh L-1 under illumination. Moreover, the
45
battery devices displayed a stable and efficient catalytic subsequently immersed into 3% H2O2, 0.5 M H2SO4, and 1
46
activity in I-/I3- redox process, maintaining a high energy M KOH at 100℃ for 1h each. Two pumps were deployed for
47
efficiency of 90% @0.2 mAcm-2 for over 80 h. the circulation of electrolytes with a constant flow rate of 8
48
mL min-1.
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2. Experimental Section
2.4 Battery tests
51
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52 2.1 Preparation of three dimensional BiVO4@TiO2/SnO2

The measurement of battery performance was conducted
53 arrays on FTO substrate on a Neware battery test station, and the AM 1.5G light
54 illumination was simulated by a 150 W Xe lamp (Zolix
The three dimensional BiVO4@TiO2/SnO2 arrays sample
55 SS150). The intensity was calibrated to 100 mW cm-2 by a
was prepared based on a colloids spheres template route
56 standard solar cell. A single cycle for cycling test comprises
combined atomic layer deposition, hydrothermal and
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57 1 h of discharging and 1 h of charging, at a current density of

electrochemical deposition techniques, the experiment
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3 0.2 and 0.5 mA cm-2. The volumetric capacity was calculated Figure 3a illustrates the configuration and working principle
4 based on the volume of electrolyte and the reaction area of of a photo-assisted ZIRFB. BiVO4@TiO2/SnO2 participate in
5 cathode. The linear sweep voltammetry and cyclic the oxidation from I- to I3-, in the electrolyte of I2/KI
6 voltammetry (CV) tests were carried out by electrochemical solution, while Zn foil functions as the anode in the alkaline
7 workstation (CS350, CS instrument). electrolyte. A cation exchange membrane is used to separate
8 two chambers and allows the free transport of K+. When the

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9 3. Results and discussion batteries undergo the charging process under illumination,
10 the photo-excited holes are transported through the
11 The scanning electron microscopy (SEM) images of 3D
photoelectrode to facilitate the oxidation from I- to I3- in
12 BiVO4@TiO2/SnO2 are shown in Figure 1a-1c. From Figure
catholyte. Meanwhile, the photo-excited electrons are
13 1a, 3D ordered hierarchical BiVO4@TiO2/SnO2 arrays with
transferred to the anode through the external circuit. The

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14 periodical structure are observed. It can be seen that SnO2
potassium ion in the electrolyte can freely migrate between
15 nanosheets decorated by TiO2 and BiVO4 are uniformly
two chambers to maintain the electrical neutrality of the
16 assembled on each microsphere. From the enlarged view in
solution. The involved charging reactions are presented as
17 Figure 1b and 1c, it can be observed that the thickness of the
18 follows:
TiO2/SnO2 nanosheets is ~50 nm, and BiVO4 nanoparticles
19 BiVO4 + hv → BiVO4 + (e- + h+) (1)
with sizes of 30 nm are clearly distributed on the surface.
20 The transmission electron microscopy (TEM) image in 3I- + 2h+ → I3- (2)

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21 Figure 1d further confirms that the decorated BiVO4 Zn(OH)42- + 2e- → Zn+ 4OH- (3)
22 nanoparticles are densely and evenly distributed on The proposed energy diagram that indicates the change of
23 TiO2/SnO2 nanosheets. The high-resolution TEM (HR-TEM) open circuit voltage (OCV) under light and dark conditions is
24 profile in Figure 1e presents the lattices of monoclinic depicted in Figure 3b. The OCV of the ZIRFBs is determined
25 BiVO4, as the interplanar spacings of 0.475 nm and 0.308 nm by the equilibrium voltage of I3-/I- relative to Zn/Zn(OH)42-
26
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correspond to the (110) and (121) planes, respectively.[28]
The (101) and (110) planes of tetragonal SnO2 are
determined by the spacings of 0.264 nm and 0.334 nm.[29]
an .[35] Under photoexcitation, the generated electrons at the
BiVO4@TiO2/SnO2 cathode cause the compression of the
potential gaps.[18] In combination with Figure 4a, the OCV
Furthermore, the SEM mapping results in Figure S2 prove of the ZIRFBs based on BiVO4@TiO2/SnO2 photocathode
30
the conformal distribution of Sn, Ti, Bi, V, O elements. falls 38 mV under simulated sunlight illumination (AM 1.5G
31
32
Based on X-ray diffraction (XRD) pattern of 100 mW cm-2), representing a narrowed potential difference
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BiVO4@TiO2/SnO2 in Figure 1f, the characteristic peaks between redox couples with photoexcitation. In Figure S3a,
33
34 corresponding to (110), (121), (040), and (002) planes of the CV profiles in 0.1 M zinc acetate, 3 M KOH and 0.1 M
35 monoclinic BiVO4 are found (PDF#14-0668). And the peaks KI confirm the redox reaction of ZIRFB. The cathodic peak
36 located at 26.6°, 33.9, 37.9, 51.8°, 61.9°, and 65.9° belong to at 0.80 V and anodic peak at -1.61 V correspond to the
37 the (110), (101), (200), (211), (310), (301) of the tetragonal oxidation of I- and the reduction of Zn2+, corresponding to
38 SnO2 (PDF#41-1445).[29] the reaction of charging process. Similarly, the peak at 0.16
39 The chemical composition and the valence state of V of KI solution and the peak at -1.42 V of ZnAc2 with KOH
40 BiVO4@TiO2/SnO2 was analyzed via X-ray photoelectron solution illustrates the redox reaction in the discharging
41 spectroscopy (XPS), as shown in Figure 2a-f. Figure 2a is process. From the linear sweeping curves in Figure 4b, the
42 the full-range spectrum of BiVO4@TiO2/SnO2, and confirms battery shows significant improvement under light condition
43 the existence of the elements Sn, Ti, Bi, V, and O. In the at a current density of lower than 4 mA cm-2, which verifies
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44 high-resolution XPS spectrum of Sn 3d. The deconvoluted the feature of photo-assisted charging light. The limited
45 peaks at 486.6 eV and 495.0 eV correspond to Sn 3d5/2 and range in current density suggests that the number of the
46 Sn 3d3/2, respectively.[30] The binding energy gap of 8.4 eV photogenerated carriers that can participate in the oxidation
47 between Sn 3d5/2 and Sn 3d3/2 further determines the Sn with reactions is finite.[36] Meanwhile, the discharge profile in
48 +4 valence in SnO2. The Ti 2p spectrum in Figure 2c reveals Figure S3b presents a slightly improved capability, reaching
49 the Ti4+ species in TiO2 according to the observed peaks at a peak power density of 6.84 mW cm-2 under light condition
50 458.7 eV and 464.6 eV.[31] Both the Bi 4f spectrum in Figure (6.80 mW cm-2 without illumination), which arises from the
51
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2d and the V 2p spectrum in Figure 2e suggest the improved conductivity of cathodes. The ZIRFB also exhibits
52 composition of BiVO4.[32, 33] As for the O 1s spectrum, the a quick response feature and excellent recoverability when
53 peak located at 529.8 eV can be attributed to the lattice switching between light and dark conditions at a current
54 oxygen.[34] The above XPS results further prove the density of 0.2 mA cm-2(Figure 4c). We further performed a
55 construction of BiVO4@TiO2/SnO2. rate experiment on both conditions, as indicated in Figure 4d.
56 Subsequently, we directly applied BiVO4@TiO2/SnO2 on The photo-assisted ZIRFBs delivers an excellent rate
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57 FTO substrate as photocathodes in the ZIRFB devices. performance ranging from 0.05 mA cm-2 to 0.5 mA cm-2.
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3 Under solar illumination, the device requires only 1.93 V to
4 reach a charge current density of 0.5 mA cm-2, compared to
5 2.27 V under dark condition. The device also shows an
6 alleviated linear relationship in Figure S4a, indicating a
7 smaller internal resistance with photo-assistance. With
8 respect to the energy efficiency under different current
After the durability test under light, the morphology and
the chemical state of BiVO4@TiO2/SnO2 cathode was
characterized, and the comparison is presented in Figure S6.
The surface of BiVO4@TiO2/SnO2 becomes passivated after
the long-time reaction, owing to the constant oxidation
reaction at the solid-liquid interface in the charge process.[41]

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9 densities in Figure S4b, the device accomplishes a 14.9% The XPS results further indicate that, apart from the lattice
10 elevation under light condition at 0.5 mA cm-2, indicating a oxygen, two extra peaks located at 531.8 eV and 533.0 eV
11 profound rate behavior. appear after the durability test, which can be attributed to the
12
The long-term operation performance of ZIRFBs is adsorbed oxygen and the adsorbed H2O.[33]
13
evaluated at a current density of 0.2 mA cm-2 (Figure 5a). The carrier transfer mechanism of the hierarchical

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From Figure 5a, the constant current charging test exhibits BiVO4@TiO2/SnO2 is revealed in Figure 6. The band
15
not only a significant lowered voltage platform by solar alignment is obtained by the optical bandgap from the UV–
16
illumination, but also a prolonged charge volumetric vis absorption spectra, and the valence band edges were
17
18 capacity. Under illumination, the charge specific capacity of measured on the basis of UPS profiles. According to the
19 BiVO4@TiO2/SnO2-based ZIRFBs is more than 150 mAh L-1 calculation from Figure S7a, the valance bands of SnO2,
20 with a low charge potential of 1.9 V. The improvement in TiO2 and BiVO4 locates at 7.35 eV, 6.65 eV, and 5.54 eV vs

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21 charge capacity can be allocated to the thorough vacuum, corresponding to 4.17 V, 3.47 V, 2.36 V versus
22 decomposition and the suppressed byproduct by Zn(OH)42-/Zn.[15, 27, 35] Based on the transmission spectra in
23 photogenerated carriers, so as to avoid the rapid clogging of Figure S7b and Kubelka-Munk formula, the band gaps of
24 the electrode.[37] The discharge specific capacity of the TiO2, SnO2, BiVO4 are calculated to be 3.61 eV, 3.18 eV,
25 battery reaches 85.5 mAh L-1 under light, compared with the 2.18 eV, respectively.[30, 31, 34] Therefore, Figure 6 describes
26 volumetric capacity of 47.6 mAh L-1 in dark. And the the working mechanism of photogenerated carriers of
27
28
29
prolonged discharge platform indicates the reduced
polarization of BiVO4@TiO2/SnO2-based ZIRFB with
illumination assistance.[16] The cycling performance is
an BiVO4@TiO2/SnO2 in ZIRFBs under illumination. The two-
step band alignments of type Ⅱ heterojunction formatted on
the photocathode can promote the charge separation and
30 another crucial indicator for evaluating the reversibility and avoid charge recombination at the interface, so as to realize
31 durability of battery devices. Here, a single cycle is the efficient oriented transfer of carriers.[27] The
32 constituted of 1 h of discharging and 1 h of charging, at a photogenerated electrons, mostly from BiVO4, are apt to
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33 current density of 0.2 mA cm-2. The BiVO4@TiO2/SnO2- move to the conduction band (CB) of SnO2, and then transfer
34 based ZIRFB device delivers great stability with the to the anode to reduce Zn(OH)42- to Zn. Simultaneously, the
35 assistance of light illumination for over 80 h, as shown in corresponding holes shift from the valance band (VB) to the
36 Figure 5c. Furthermore, the boost of light in energy solid-liquid interface, to participate in the oxidation of I-,
37 efficiency is enormous. An extreme high energy efficiency of because the VB potential of BiVO4 (2.36 V) is more positive
38 94% at the 5th cycle is achieved, outperforming the ZIRFBs than the I-/I3- redox potential (1.79 V versus Zn(OH)42-
39 under dark condition by 11%. The energy efficiency under /Zn).[20] As a result, the BiVO4@TiO2/SnO2 facilitates the
40 light remains at 90% after 80 h, while the performance of redox reaction efficiency of iodine redox couples, and further
41 ZIRFB device rapidly decays in dark, retaining only an enhances the battery performance under illumination.
42
efficiency of 73%. Moreover, the BiVO4@TiO2/SnO2-based
43
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ZIRFB device achieves a stable cycling performance with the 4. Conclusion

44
charge and discharge potential plateaus at ~2.05 V and ~1.68
45 Three-dimensional BiVO4-based ternary semiconductor
V, respectively, under illumination for 80 h at 0.5 mA cm-2
46 photoelectrodes are realized and further applied in the
(Figure S5). As for the energy efficiency, the device
47 ZIRFBs as photo-assisted cathodes. The BiVO4@TiO2/SnO2
48 accomplishes ~14.6% elevation under light conditions at 80
is advantageous as photocathode due to favorable carrier
49 h. Compared with recently-reported literatures on photo-
transfer capability and the highly exposed active surface area
50 assisted redox batteries in Table S1, our BiVO4@TiO2/SnO2-
of three-dimensional hierarchical structure. The boosted I-
51 based ZIRFB still achieves comparable improvement to
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oxidation kinetics under illumination significantly reduced

52 energy efficiency of batteries. And the performance is
the charge voltage and enhanced energy efficiency. In
53 expected to be further enhanced by the construction of three-
addition, the ZIRFBs based on BiVO4@TiO2/SnO2
54 dimensional semiconductor material systems with higher
photoelectrodes accomplished an extended volumetric
55 performance, such as TaON,[38] Ta3N5,[39] WO3[40] under the
capacity and a satisfying long-term stability under light. Our
56 enlightenment of the present work.
research demonstrates that the introduction of well-designed
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57 photoelectrodes has broad prospect in the advancement of

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3 Zn-based aqueous batteries with high energy efficiency by [25] Wang Z, Chiu H C, Paolella A, Zaghib K and Demopoulos G
4 the utilization of solar energy. P, 2019 ChemSusChem 12 2220
5 [26] Zhang H and Cheng C, 2017 ACS Energy Lett. 2 813
6 Acknowledgements [27] Pan Q, Li A, Zhang Y, Yang Y and Cheng C, 2020 Adv. Sci. 7
7 1902235
8 This work is financially supported by the National Natural [28] Park E, Patil S S, Lee H, Kumbhar V S and Lee K, 2021

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9 Nanoscale 13 16932
Science Foundation of China (Grant No. 51772213) and
[29] Liu J, Li J, Shao M and Wei M, 2019 J. Mater. Chem. A 7
10 Fundamental Research Funds for the Central Universities. 6327
11
[30] Kim J H, Choi I Y, Kim J H, Kim J, Kim Y K, Kim J K and
12 References Lee J S, 2021 Small 17 2103861
13 [31] Wang L, Si W, Ye Y, Wang S, Hou F, Hou X, Cai H, Dou S X

cri
14 [1] Li Y, Gong M, Liang Y, Feng J, Kim J E, Wang H, Hong G,
Zhang B and Dai H, 2013 Nat. Commun. 4 1805 and Liang J, 2021 ACS Appl. Mater. Interfaces 13 44184
15 [32] Liu C, Zhou J, Su J and Guo L, 2019 Appl. Catal., B 241 506
[2] Bae D, Kanellos G, Faasse G M, Drazevic E, Venugopal A and
16 [33] Ma C, Lee J, Kim Y, Cheol Seo W, Jung H and Yang W, 2021
Smith W A, 2020 Commun. Mater. 1 17
17 [3] Bae D, Faasse G M, Kanellos G and Smith W A, 2019 J. Colloid Interface Sci. 581 514
18 Sustainable Energy Fuels 3 2399 [34] Lai C, Zhang M, Li B, Huang D, Zeng G, Qin L, Liu X, Yi H,
19 [4] Xie C, Zhang H, Xu W, Wang W and Li X, 2018 Angew. Cheng M, Li L, Chen Z and Chen L, 2019 Chem. Eng. J. 358
20 Chem., Int. Ed. Engl. 57 11171 891

us
21 [5] Xu P, Chen H, Zhou X and Xiang H, 2021 J. Membr. Sci. 617 [35] Zhang J, Jiang G, Xu P, Ghorbani Kashkooli A, Mousavi M,
22 118660 Yu A and Chen Z, 2018 Energy Environ. Sci. 11 2010
[36] Yang W, Li F, Liu H, Li Z, Zhao J and Wang Y, 2021 New J.
23 [6] Deng Y-P, Liang R, Jiang G, Jiang Y, Yu A and Chen Z, 2020
Chem. 45 21160
24 ACS Energy Lett. 5 1665
[37] Wang H, Cao J, Zhou Y, Wang X, Huang H, Liu Y, Shao M
25 [7] Chen G, Xu Y, Huang L, Douka A I and Xia B Y, 2021 J.
and Kang Z, 2021 Nano Res. 14 3886
26 Energy Chem. 55 183
27
28
29
[8]

[9]
Bai C, Cai F, Wang L, Guo S, Liu X and Yuan Z, 2018 Nano
Res. 11 3548
Pei Z, Zhu Z, Sun D, Cai J, Mosallanezhad A, Chen M and
an [38] Hou J, Cheng H, Takeda O and Zhu H, 2015 Energy Environ.
Sci. 8 1348
[39] Wang Q, Ma X, Wu P, Li B, Zhang L and Shi J, 2021 Nano
Wang G, 2021 Mater. Res. Bull. 141 111347 Energy 89 106326
30 [10] Mousavi M, Jiang G, Zhang J, Kashkooli A G, Dou H, Silva C [40] Shi X, Dong F, Dai C, Ye X, Yang P, Zheng L and Zheng H,
31 J, Cano Z P, Niu Y, Yu A and Chen Z, 2020 Energy Storage. 2020 Electrochim. Acta 361 137017
32 [41] Lee D K and Choi K-S, 2017 Nat. Energy 3 53
dM
Mater. 32 465
33 [11] Mousavi M, Dou H, Fathiannasab H, Silva C J, Yu A and
34 Chen Z, 2021 Chem. Eng. J. 412 128499
35 [12] Zhu D, Zhao Q, Fan G, Zhao S, Wang L, Li F and Chen J,
36 2019 Angew. Chem., Int. Ed. Engl. 58 12460
37 [13] Man Y, Hao Q, Chen F, Chen X, Wang Y, Liu T, Liu F and Li
38 N, 2019 ChemElectroChem 6 5872
39 [14] Yu M, Ren X, Ma L and Wu Y, 2014 Nat. Commun. 5 5111
40 [15] Liu X, Yuan Y, Liu J, Liu B, Chen X, Ding J, Han X, Deng Y,
41 Zhong C and Hu W, 2019 Nat. Commun. 10 4767
[16] Tian Z, Li C, Cai J, Zhang L, Lu C, Song Y, Jiang T, Sun J and
42
Dou S, 2019 Chem. Commun. 55 1291
43
pte

[17] Fang Z, Zhang Y, Hu X, Fu X, Dai L and Yu D, 2019 Angew.

44 Chem., Int. Ed. 58 9248
45 [18] Nikiforidis G, Tajima K and Byon H R, 2016 ACS Energy Lett.
46 1 806
47 [19] Qiao Y, Liu Y, Jiang K, Li X, He Y, Li Q, Wu S and Zhou H,
48 2017 Small Methods 1700284
49 [20] Liu Y, Li N, Liao K, Li Q, Ishida M and Zhou H, 2016 J.
50 Mater. Chem. A 4 12411
51
ce

[21] Li M, Wang X, Li F, Zheng L, Xu J and Yu J, 2020 Adv.

52 Mater. 32 1907098
53 [22] Chen P, Li G R, Li T T and Gao X P, 2019 Adv. Sci. 6
54 1900620
[23] Feng H, Jiao X, Chen R, Zhu X, Liao Q, Ye D, Zhang B and
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Zhang W, 2019 J. Power Sources 419 162
56
[24] Zhao W, Wang X-F, Zheng E, Wei Y, Sanehira Y and Chen G,
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Figure 1. (a-c) SEM images of BiVO4@TiO2/SnO2. (d) TEM image and (e) HR-TEM image of BiVO4@TiO2/SnO2. (f) XRD
pattern of BiVO4@TiO2/SnO2
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24 Figure 2. XPS spectra of BiVO4@TiO2/SnO2. (a) full-range spectrum, (b) Sn 3d, (c) Ti 2p, (d) Bi 4f, (e) V 2p, (f) O 1s.
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21 Figure 3. (a) Schematic illustration of working mechanism of the photo-assisted ZIRFB. (b) Proposed energy diagram of OCVs under light
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Figure 4 (a) Open circuit voltage without (grey area) and with (yellow area) illumination (b) Charge polarization curves. (c) Light-response
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Figure 5 (a) Volumetric capacity under light and dark conditions. (b) Energy efficiency of and (c) cycling performance at current density of
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0.2 mA cm-2 under dark and light conditions of Zn-I2 battery
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