Chemical Engineering Journal 433 (2022) 133559

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

Rechargeable sunlight-promoted Zn-air battery constructed by bifunctional

oxygen photoelectrodes: Energy-band switching between ZnO/Cu2O and
ZnO/CuO in charge-discharge cycles
Degang Bu a, 1, Munkhbayar Batmunkh b, 1, Yu Zhang a, 1, *, Yuewen Li a, Bingzhi Qian a,
Yalin Lan a, Xing Hou a, Shuo Li a, Baohua Jia c, Xi-Ming Song a, *, Tianyi Ma c, *
a
Liaoning Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials, College of Chemistry, Liaoning University, Shenyang 110036, PR China
b
Centre for Catalysis and Clean Environment, School of Environment and Science, Griffith University, Gold Coast, Queensland 4222, Australia
c
Centre for Translational Atomaterials, Swinburne University of Technology, Hawthorn, Victoria 3122, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: Effective utilization of solar energy in battery systems has become an active attractive and active research in the
Sunlight promotion strategy field of green energy. Herein, highly efficient and stable bifunctional oxygen reduction reaction (ORR) and
Bifunctional catalyst oxygen evolution reaction (OER) photoelectrodes are constructed for rechargeable Zn-air batteries. This work
ZnO/CuO heterostructure
introduces a simple and efficient method for designing bifunctional ZnO/CuO composite materials with
Zn-air battery
impressive photocatalytic activity, superhydrophilicity and excellent stability. Through the strategy of sunlight
promotion, the ZnO/CuO photoelectrodes are used in the charging and discharging processes of Zn-air batteries,
achieving low charge potential and high discharge potential of around 1.50 V and 1.28 V by galvanostatic charge
and discharge, respectively. Under illumination, the short-circuit current and open-circuit voltage can reach up
to 49 mA cm-2 and 0.9 V, respectively. We revealed that this bifunctionality is originated from the valence change
mechanism of Cu, meaning that ZnO/Cu2O and ZnO/CuO play the photoelectric catalytic roles in charge and
discharge processes, respectively. This work paves the way to introduce a facile and efficient method for the
development of integrated single-cell photo-assisted Zn-air batteries.

1. Introduction single device

Among the various types of secondary batteries, Zn-air battery is
Nowadays, the development of new energy storage technologies considered as a promising new energy storage technology due to its
with high safety, high stability and low cost is in urgent demand. advantages of high theoretical energy density, high safety and low cost
Renewable energy technologies including solar and wind energies have [6,7]. It is mainly composed of metal zinc electrode, air electrode which
become promising alternatives to replace the traditional fossil fuels can support oxygen reaction, and electrolyte with corresponding con­
[1–3]. However, the major drawback of renewable technologies such as ductivity [8,9]. The battery provides electricity through the oxidation-
solar or wind energy is that they only convert sunlight energy into reduction reaction between oxygen and metal anode, and its reaction
instant electricity for immediate usage, and cannot store energy in a mechanism is similar to that of a fuel cell [10–12]. Although the
single battery system [4]. For practical applications, photovoltaic (PV) rechargeable Zn-air batteries have undergone decades of exciting evo­
cells must be matched with energy storage batteries to make better use lution, there are still some problems to be solved. One of the most sig­
of renewable energy [5]. Therefore, in recent years, researchers nificant challenges in this cutting-edge technology is the fact that the
explored the opportunities of light-assisted energy storage batteries. charge and discharge performance of Zn-air batteries is limited by the
Some part of the energies in the charging process comes from solar en­ slow oxygen release and oxygen reduction kinetics of air electrode
ergy, which can greatly reduce the over-charge potential in battery [13,14]. Therefore, novel types of air cathode bifunctional catalysts
systems, so as to realize the utilization and storage of solar energy in a should be developed to realize high rechargeability that can facilitate

* Corresponding authors.
E-mail addresses: zhangy@lnu.edu.cn (Y. Zhang), songlab@lnu.edu.cn (X.-M. Song), tianyima@swin.edu.au (T. Ma).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.cej.2021.133559
Received 27 August 2021; Received in revised form 18 October 2021; Accepted 6 November 2021
Available online 14 November 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
D. Bu et al. Chemical Engineering Journal 433 (2022) 133559

both Oxygen reduction reaction (ORR) during discharging and Oxygen stirred for 30 min at room temperature. After the addition of 1 g glucose,
evolution reaction (OER) during charging processes [15]. the obtained blue suspension was heated at 60 ◦ C for 30 min under
The introduction of light energy into electrochemical devices pro­ stirring. The obtained red slurry was centrifuged with water and
vides a promising and environmentally friendly energy conversion and ethanol, and then dried at 60 ◦ C for 12 h [24].
storage devices with improved reaction kinetics and reduced over­
potentials [16–18]. It usually involves the application of semiconductor 2.3. Synthesis of ZnO
materials, which are excited by photon to produce photogenerated
charges (e.g. electrons and holes); and these charge carriers are then The ZnO nanorods were prepared using a hydrothermal method,
transferred to participate in the oxidation-reduction reactions. Recently, Firstly, 0.1 M Zn(NO3)2⋅6H2O was dissolved in 50 mL of H2O, then 4 mL
there have been few reports on light-assisted metal-air batteries. For of ammonia was added drop by drop while stirring. Then the sample was
example, Du et al [19]. reported a Zn-air battery with two cathodes of put into Teflon-lined stainless steel autoclave, which was sealed and
poly(1,4-di(2-thienyl))benzene (PDTB) and TiO2 grown on carbon pa­ heated at 90 ◦ C for 12 h. After cooling to room temperature, the sample
pers to sandwich a zinc anode. The reported TiO2 and PDTB promoted was rinsed with deionized water and ethanol for 2 times, followed by
Oxygen evolution reaction (OER) and Oxygen reduction reaction (ORR), drying in an oven at 80 ◦ C overnight.
respectively, during charging and discharging processes under illumi­
nation. In 2018, Lv et al [20]. proposed an effective photocathode-based 2.4. Prepared of CuO/ZnO electrode
rechargeable Zn-air battery, which used a p-n heterojunction as an
efficient photo absorbent for improved voltage. However, the majority The ZnO/CuO film was loaded on a FTO substrate via a facile solid-
of the available reports have focused on the photo-assisted charge, with state reaction strategy. Firstly, 20.0 mg ZnO and 20.0 mg Cu2O were
very few studies involving photo-assisted discharge [12,21], while still mixed and ultrasonically dispersed in 6 mL ethylene glycol to obtain a
requiring an external air electrode. There are few reports on single homogeneous suspension. Then, 0.5 mL of the above slurry was dropped
electrodes with photo-assisted bifunctions [20]. And Table 1 presents onto the FTO surface, followed by doctor-blading to obtain smooth film.
the other sunlight-promoted batteries. Then, the film was calcined in a muffle furnace at 400 ◦ C (2 ◦ C/min) for
Our previous theoretical study found that the heterostructure is 1 h, followed by cooling to room temperature. The procedure was
helpful to improve the utilization of visible light and the band bending to repeated three times to obtain the final photoelectrode.
facilitate the charge separation, resulting from an alignment of Fermi
levels [22]. Considering this, creating heterojunction is expected to be 2.5. Characterization
effective for the construction of bifunctional light responsive electro­
catalysts. In this work, we designed a photo-assisted rechargeable Zn-air The X-ray diffraction (XRD) patterns were obtained on a Bruker
battery composed of superhydrophilic ZnO/CuO photoelectrode, which (Germany) D8 Advance diffractometer using Cu K α radiation in the
also exhibit bifunctional photo-assisted charging and discharging abili­ range of 20-80 (θ). The morphologies of the films were observed using a
ties benefited from the heterostructure. We revealed that the valences of scanning electron microscope (SEM, Shimadzu JSM-6700F). UV-vis
Cu+ and Cu2+ form Cu2O/ZnO and CuO/ZnO heterostructures during diffuse reflectance spectroscopy (DRS) measurements were obtained on
the charging and discharging processes, respectively, which promote the the semiconductor films using an UV-vis spectrometer (Shimadzu UV-
separation and transport of photo-generated holes and electrons. This 2550) and converted from reflection to absorbance by the Kubelka-
promising system promises to be a facile and cost-effective energy Munk method. The light source was provided by a 500 W Xenon lamp
conversion and storage device with excellent bifunctionalities [23]. The (CHFXQ500W, Beijing Trusttech Co. Ltd.) and a filter plate (AM 1.5,
n-type ZnO and p-type CuO are the catalytic active sites for the OER and Beijing Perfectlight Technology Co. Ltd.). The output light intensity was
ORR, respectively. calibrated to be 100 mW cm− 2, which was measured with a radiometer
The results show that the low charge potential and high discharge (Photoelectronic Instrument Co. Attached to Beijing Normal University,
potential of around 1.50 V and 1.28 V under illumination, respectively, China). The Surface photovoltage (SPV) transient measurement was
can be obtained by using the photoelectrode with double catalytic ac­ performed in air atmosphere at indoor temperature. The sample-
tivities as the air electrode under illumination. The light-induced charge chamber-like parallel-plate capacitor was composed of the sample film
potential lowered by 0.77 V as compared to the typical charge voltage of on the FTO substrate, a piece of 10 mm-thick mica, and a platinum wire
~ 2 V in a conventional Zn-air battery, while the discharge potential gauze electrode. A 355 nm laser pulse (50 mJ cm− 2) of 10 ns width was
increased by about 0.65 V as compared with the dark condition (0.63 V). used to excite the sample, and the PV signal was recorded in the range
Meanwhile, the photoelectrochemical properties of ZnO/CuO in the Zn- from 100 ns to 10 ms. The surface structure of the samples film were
air batteries are studied through electrochemical and PV methods; and measured using an Agilent 5100 Atomic force microscopy (AFM). The
photogenerated charge transfer diagram is established. contact angle measurements were obtained using a DSA 100 Kruss
contact angle meter. Fluorescence measurements were executed on a
2. Experimental Section fluorescence spec-trophotometer (RF-5301PC, SHIMADZU, Japan).

2.1. Chemicals 2.6. Photoelectrochemical measurements

All chemicals were analytical grade and used without further puri­ To investigate the catalytic activity of the ZnO/CuO, Linear sweep
fication. The chemicals used in the work were copper nitrate trihy­ voltammetry (LSV) was employed to evaluate the Oxygen reduction
drate, glucose, sodium hydroxide, potassium hydroxide, ethanol, reaction (ORR) and Oxygen evolution reaction (OER) performance in
ethylene glycol, zinc nitrate hexahydrate and ammonia (25 wt%), which 1.0 M KOH solution. The potentials used in this work with respect to the
were purchased from Sinopharm Chemical Re-agent Company. Fluorine- Ag/AgCl electrode was converted to the potential versus the Reversible
doped tin oxide (FTO) glass substrates were purchased from PV Tech hydrogen electrode (RHE) according to E(RHE) = E(NHE) + 0.059 pH; E
Company. (NHE) = E(Ag/AgCl) + 0.197. Mott-Schottky (MS) plots were used to
determine the flat band (FB) potentials of ZnO, CuO and ZnO/CuO
2.2. Synthesis of Cu2O performance in 0.5 M Na2SO4 solution through Mott-Schottky (MS)
plots, and the frequency of the MS method was 1 KHz. The above tests
0.1 M Cu(NO3)2⋅3H2O was dissolved in 50 mL of H2O, and then 10 were performed on electrochemistry workstation (CHI660E, Shanghai
mL of NaOH solution (3 M) was added drop by drop and the mixture was Chenhua Instrument Co., Ltd.) in a three-electrode system, where the

2
D. Bu et al. Chemical Engineering Journal 433 (2022) 133559

Fig. 1. Working mechanism of the photo-assisted rechargeable Zn-air battery.

films on FTO was used as the working electrode, and Ag/AgCl and Pt as the counter electrode in a mixed solution (1 M KOH and 0.02 M Zn
wire were used as the counter and reference electrode, respectively. (AC)2⋅6H2O). Through 3D printing technology, we designed a brand
Chronopotentiometry and EIS were tested in a two-electrode system new photo-assisted battery device and conducted performance tests.
including the ZnO/CuO film as the working electrode and the metal zinc

Fig. 2. (a) The formation process of the ZnO/CuO. (b) FESEM image of ZnO Nanoclusters. (c) FESEM image of Cu2O octahedra. (d) FESEM image of ZnO/CuO film
and cross section view of ZnO/CuO film (inset). (e) Elemental mapping images of ZnO/CuO film.

3
D. Bu et al. Chemical Engineering Journal 433 (2022) 133559

Fig. 3. (a) XRD patterns of ZnO/CuO film on FTO. (b) UV-vis DRS of ZnO, CuO and ZnO/CuO films. (c) The plots of (Ahν)2 vs. photon energy of ZnO and the plots of
(Ahν) 2 vs. photon energy of CuO. (d) Photoluminescence spectra of ZnO, CuO and ZnO/CuO. (e) SPV transients of the ZnO, CuO and ZnO/CuO films excited by 355
nm laser pulse. (f) SPV amplitude of the ZnO, CuO and ZnO/CuO films. (g) SPV phase spectra of the ZnO, CuO and ZnO/CuO films. (h) Contact angle measurement of
ZnO/CuO film. (i) Comparison of electrolyte-permeable and nonpermeable catalyst layers.

Air electrode: ZnO/CuO + hν → e− + h+

3. Results and Discussion
O2 + 2 H2O + 4 e− → 4 OH− E0 = 0.401 V versus SHE
Fig. 1 illustrates the basic structure and working mechanism of
rechargeable Zn-air battery based on sunlight promotion strategy. It is side-reaction: 2 e− + 2 CuO + H2O → Cu2O + 2 OH−
mainly composed of metal zinc as the negative electrode and semi­ Overall: 2 Zn + O2 → ZnO E0 = 1.65 V
conductor photoelectrode as the air electrode, and has been assembled
in a pouch battery with alkaline electrolyte. Different from the charging Charge process:
and discharging processes of the traditional Zn-air battery, the semi­
Zinc electrode: ZnO + H2O + 2 e− → Zn + 2 OH−
conductor photoelectrode is excited by the light energy to generate
photo-generated electrons and holes, which can then participate in the Air electrode: ZnO/Cu2O + hν → e− + h+
ORR and OER reactions in discharge and charge process, respectively.
Based on in-situ XRD results, the bifunctional photoelectrode is 4 OH− + 4 h+ → 2 H2O + O2
accompanied by the mutual conversion of ZnO/CuO and ZnO/Cu2O
side-reaction: Cu2O + 2 h+ + 2 OH− → 2 CuO + H2O
heterostructures in the discharging and charging processes, respectively,
which demonstrates the full utilization of light for the respective ORR The FESEM images of ZnO nanoclusters, CuO octahedral structures
and OER. The reactions at the ZnO/CuO air electrode and zinc electrode and ZnO/CuO composites are shown in Fig. 2b–d, which were synthe­
in the photo-assisted rechargeable Zn-air battery is illustrated as follows sized via the procedures schematically illustrated in Fig. 2a. The doctor
[9,19]: blade technique was used to prepare the uniform ZnO/CuO layer on the
Discharge process: Fluorine-doped tin oxide (FTO) glass substrate. It can be seen from
Fig. 2b that the ZnO is a nanocluster structure composed of 1～1.5 µm
Zinc electrode: Zn + 4 OH− → Zn(OH)42− + 2 e- E0 = − 1.25 V versus SHE
nanorods. Fig. 2c indicates that the CuO has an irregular octahedral
Zn(OH)42− → ZnO + H2O + 2 OH− structure with an average diameter of ~ 1 µm. As shown in Fig. 2d, ZnO
and CuO are well hybridized; and the part of CuO is closely attached

4
D. Bu et al. Chemical Engineering Journal 433 (2022) 133559

Fig. 4. DMPO spin-trapping ESR technique used to measure (a) •O2- and (b) •OH generated during ORR and OER production. Mott-Schottky curves of (c) ZnO, (d)
CuO, (e) ZnO/CuO thin films. (f) ORR polarization curves of ZnO/CuO with and without illumination. (g) OER polarization curves of ZnO/CuO with and without
illumination. (h) Cyclic voltammetry curve of zinc electrode.

onto the surface of ZnO, the thickness of the resulting film was about 23 Fig. 3a shows the XRD patterns of the ZnO/CuO composite. After
µm. The elemental mapping (Fig. 2e) and EDS (Fig. S1) reveal the removing the diffraction peaks of FTO, the diffraction peaks of CuO are
coexistence of Cu, Zn and O elements, confirming the successful fabri­ in agreement with the reference pattern (JCPDS No.45–0937) [25]. Two
cation of ZnO/CuO. The as-synthesized structures are in micron-sizes, relatively strong peaks appeared at 28.9◦ and 30.5◦ can be assigned to
which are expected to facilitate the penetration of the electrolyte in the (002) and (111) orientations of CuO, respectively. The diffraction
the film, and enable the photo-generated charges to fully react with the peaks centered at 31.8◦ , 34.4◦ , 36.3◦ , 47.5◦ and 62.9◦ can be assigned to
electrolyte in ORR and OER. Meanwhile, we characterized the surface the characteristic peaks of the standard hexagonal wurtzite ZnO struc­
morphology of the zinc electrode before and after charging and dis­ ture (JCPDS No. 36-1451) [26]. The strong (101) diffraction peak in­
charging processes (Supplementary Fig. S2 and Fig. S3). We found that dicates the preferred orientation of ZnO nanorods on the (101) plane
the surface of the zinc electrode after charging and discharging pro­ [27]. As the two samples were physically mixed (see Fig. 2d), the peak
cesses was covered with a layer of hollow microrod structure. The belt intensities of ZnO and CuO were relatively stable with no significant
edge presents a regular hexagonal structure, and the diameter of the impurity peak, indicating that they have been uniformly doped.
hollow part was measured to be around 2.7 μm (Fig. S2). The micron- The optical characteristics of ZnO, CuO and ZnO/CuO were inves­
level hollow structure provides an opportunity to construct novel ar­ tigated using a ultraviolet–visible (UV–vis) Diffuse reflectance spectra
chitectures such as packed catalyst structure. As shown in the XRD (DRS) as shown in Fig. 3b. The absorption threshold of ZnO and CuO are
patterns before and after charging and discharging processes (Fig. S4), located at 410 nm and 900 nm, respectively. It can be seen that the
the diffraction peak at 33.5◦ , which corresponds to the (111) crystal absorption region of CuO includes UV, visible, and near-infrared re­
plane of ZnO (JCPDS 65-2880), can be observed. The experimental gions. ZnO/CuO also has absorption spectrum range from 410 nm to
phenomenon that we first discovered in the battery reaction opens up a 900 nm. The absorption intensity of ZnO/CuO was higher than that of
new research avenue for further exploration. ZnO and CuO, indicating that CuO effectively improves the visible light

5
D. Bu et al. Chemical Engineering Journal 433 (2022) 133559

Fig. 5. Electrochemical characterizations of the sunlight-promoted rechargeable Zn–air battery. (a) I-V curves of Zn-air battery with and without illumination. (b) V-
P curves of Zn-air battery with and without illumination. Under 0.1 mA cm− 2 current density (c) the charge curves of a Zn–air battery in the dark and under
illumination were studied by ZnO/CuO air photoelectrode, respectively. (d) the discharge curves of a Zn–air battery in the dark and under illumination were studied
by ZnO/CuO air photoelectrode, respectively. (e) The charge voltage curves of a Zn-air battery under illumination were studied by ZnO/CuO air photoelectrode,
respectively, at the current density ramp (0.05-2 mA cm− 2). (f) The discharge voltage curves of a Zn-air battery under illumination were studied by ZnO/CuO air
photoelectrode, respectively, at the current density ramp (0.5-2 mA cm− 2). (g) Long-term charge and discharge performance test. (h) Cycle stability test of
rechargeable Zn-air battery.

utilization of ZnO. In addition, the successful coupling of ZnO and CuO properties. To further study the semiconductor conductivity type and
was further demonstrated at the absorption threshold of 420 nm. The charge transfer kinetics, we carried out transient photovoltage and
corresponding band-gap energies can be estimated from the Tauc’s plots steady-state SPV measurements on the semiconductor electrodes. Ac­
by (αhν) = B(hν-Eg)n/2, where B, n and Eg represent the constant, light cording to Fig. 3e, the ZnO electrode shows a positive SPV transient
frequency and energy band gap, respectively[28], and n depends on signal, indicating its n-type conductivity in which photogenerated
whether the transition is direct (n = 1) or indirect (n = 4). ZnO and CuO electrons are moved to the bottom electrode and photogenerated holes
are both direct band gap semiconductors; and the band gap of ZnO and accumulated at the surface[31]. Both CuO and ZnO/CuO electrodes
CuO were calculated to be 3.18 eV and 1.37 eV, respectively (Fig. 3c). show negative signals, which confirm their p-type conductivity. It can be
According to previous reports [29,30], the Conduction band (CB) level seen that ZnO recombined in 5.5 × 10− 7 s and CuO recombined
position (Ec) of ZnO and CuO are − 0.78 V and − 0.65 V respectively (vs. completely in 8.2 × 10− 5 s, whereas the ZnO/CuO composite material
Ag/AgCl), and the Valence band (VB) level (Ev) can be obtained by the produced a diffusion peak after 5.5 × 10− 4 s and its PV signal lasted for
equation Ec = Ev− Eg. Fig. 3d shows the photoluminescence (PL) spectra 0.005 s. According to the time scale of signal disappearance (reach 0
of ZnO, CuO and ZnO/CuO. The decreased PL signal for the ZnO/CuO μV), the lifetime of the photogenerated carriers of ZnO/CuO composite
hybrid with respect to the pure ZnO, and its PL signal is between the was longer than that of only CuO, indicating that the structure of the
pure ZnO and the pure CuO, suggesting that the recombination of photo- heterogeneous interface greatly reduced the recombination of photo­
generated electron-hole pairs of ZnO was effectively suppressed by generated electrons and holes. As depicted in Fig. 3f, ZnO and CuO
incorporating p-type CuO, while interfacial charge separation existing in mainly have SPV bands in the UV and visible regions, respectively.
the heterostrucure can also help to improve the charge transporting However, the SPV band of the ZnO/CuO heterostructured film exists in

6
D. Bu et al. Chemical Engineering Journal 433 (2022) 133559

the entire UV and visible regions, which proves that the ZnO/CuO film ZnO/CuO electrode exhibits a higher initial potential of around 1.4 V
has a good solar utilization efficiency. To further study the separation (vs. RHE) in dark condition, which is higher than the potential for water
direction of the photogenerated charge carriers in a steady state, the SPV oxidation. On the contrary, the onset potential of the ZnO/CuO elec­
phase spectra were measured and are displayed in Fig. 3g. According to trode under illumination was significantly reduced to 0.9 V (vs. RHE).
previous reports [32,33], when the phase degrees located from -90◦ to Similarly, the initial potential of oxygen reduction of the ZnO/CuO
90◦ , the n-type semiconductor feature may exist if photogenerated electrode under illumination (0.57 V vs. RHE) was 0.27 V (vs. RHE)
negative charges are closer to the FTO and positive charges are nearby higher than that under dark state (0.3 V vs. RHE). The above verification
the surface of the material. On the other hand, when the phase degrees shows that the ZnO/CuO electrode material has bifunctional photo­
located in the other quadrant, (− 180◦ ~ − 90◦ , 90◦ ~180◦ ), the p-type electric catalytic activity. As illustrated in Fig. 5a and 5b, the charging
semiconductor feature may exist if the positive charges are near by the and discharging of the Zn-air battery under light and dark state can be
FTO and photogenerated negative charges transfer to the surface of the further verified. As shown in Fig. 4h, the oxidation potential of the metal
material. The PV signal further proves that the accumulation of photo- zinc electrode was -0.4 V, whereas the oxidation peak at 1.4 V is
generated holes on the surface of ZnO is beneficial to the OER reac­ attributed to the oxidation of water. The open circuit voltage (Voc) of Zn-
tion, and the electron accumulations on the surface of CuO can be air batteries should be determined by the electrochemical potential
effective to the ORR process. The hydrophilicity of semiconductor difference between the air electrode and metal electrode reactions.
electrode is also a key factor affecting the electrode reaction. Fig. 3h and Therefore, the difference between the oxidation potential of zinc (− 0.4
Fig. S5 show the contact angles of ZnO/CuO and ZnO/Cu2O films, V vs. RHE) and the light-induced ORR reduction potential (0.57 V vs.
respectively, revealing that they have super-hydrophilic surfaces with RHE) was about 0.97 V, which should be equal to the theoretical voltage
contact angles of 16.5◦ and 15.5◦ , respectively. In order to further of our battery. Combined with Fig. 5a, the Voc of Zn-air battery under
confirm the surface structure of the semiconductor film, atomic force dark state and simulated light was determined to be 0.72 V and 0.9 V,
microscopic (AFM) analysis was performed. Fig. S6 shows that the sur­ respectively, which are basically equal to the potential difference of ORR
face of ZnO is smooth, indicating that ZnO is attached to the FTO surface and zinc oxidation reaction.
with a relatively dense array structure. The surface of CuO is relatively As shown in Fig. 5a, the photo-assisted Zn-air battery exhibits an Voc
coarse, which is due to the irregular block structure of CuO (Fig. S7). of 0.9 V under illumination, which is consistent with the result of the Voc
And ZnO/CuO has more obvious surface roughness (Fig. S8). The elec­ calculated earlier. The J-V and P-V curves show that the Zn-air battery
trolyte can effectively penetrate into the catalyst layer to improve the displayed a short-circuit current (Jsc) of 49 mA cm-2 and a peak power
electrical and ionic conductivity of the solid catalyst. The formed density of 7.8 mW cm− 2 (Fig. 5b). The charge curves of the Zn-air bat­
“adaptive junction” can provide improved efficiency (Fig. 3i left). The tery based on the ZnO/CuO photoelectrode in the dark and light are
“buried heterojunctions” formed by dense catalysts are often limited by shown in Fig. 5c and 5d, respectively. The Zn-air battery has a high
Fermi-level pinning and low photovoltages (Fig. 3i right). These results charge potential of 2.27 V in the dark conditions. However, the charge
elucidate a design principle for catalyzed photoelectrodes and provides voltage under light illumination was significantly reduced to 1.5 V,
important references for the design of photocatalytic electrodes[34]. which is lower than the theoretical charge voltage of 1.6 V for Zn-air
The Electron paramagnetic resonance (EPR) is a powerful technique battery. Correspondingly, the discharge voltage of a Zn-air battery
to examine free radicals[35]. In this photocatalytic system, the free under light was 1.28 V, which is about 0.65 V higher than that in the
radicals •OH and •O2- generated during photocatalytic reactions were dark conditions (~0.63 V). This means that the energy efficiency has
further verified by 5,5-dimethy-1-pyrroline N-oxide (DMPO) spin- been more than doubled. According to Fig. S10, the specific capacity and
trapping EPR spectra. As shown in Fig. 4a and 4b, no intermediates the energy density of battery is 333.5 mAh/g by the Equation S2. Fig. 5e
were captured under dark state conditions. However, the characteristic and 5f show the charge and discharge curves of a Zn-air battery pro­
peaks of DMPO-•O2− and DMPO-•OH signals were detected under moted by sunlight under different current density conditions. When the
visible light irradiation, corresponding to the two typical EPR signals current density is 0.1 mA cm-2, the battery charging voltage was 1.5 V.
with an intensity ratio of 1:1:1:1 and 1:2:2:1[36], respectively. This As the current density increases, the charge voltage increases accord­
result further proves that the separated photo-generated electrons and ingly, but both of them are significantly lower than the charge potential
photo-generated holes will further react with O2 to produce •O2-and in the dark conditions. The discharging process was diametrically
H2O to •OH respectively. In order to better understand the ORR process, opposite to the charging process, and the battery discharge voltage
rotating disk electrodes were employed under 200-1800 rpm conditions decreased as the current density increased. At the same current density,
to evaluate the number of transferred electrons during the ORR process. the discharge (charge) voltages under light are significantly higher
As shown in Fig. S9, both the ring current and the disk current of ZnO/ (lower) than the charge and discharge voltages in the dark. At the same
CuO increase with the increase of the rotation speed, and the number of time, the Power conversion efficiency (PCE) at different current den­
electron transfer is derived from the S1 equation. The ORR on ZnO/CuO sities based on Equation S3 is shown in Fig. S11. In order to prove the
occurs via a 2e- process, which is consistent with the result of EPR. practical application of Zn-air battery, we conducted charging and dis­
The flat band potential of semiconductors was calculated by Mott- charging tests every 20 min (Fig. 5g). The stable charge and discharge
Schottky (M-S) equation. The linear relationship between 1/C2 and platform indicates that the OER and ORR reactions can be carried out
applied voltage can be observed from Fig. 4c and 4d. It can be seen that effectively and continuously. In order to exclude the influence of FTO,
ZnO and CuO show a positive slope and a negative slope, respectively, the charging and discharging test was conducted by using a pure FTO as
which indicate that ZnO is an n-type semiconductor with electrons as the an air electrode under illumination. As a result, the FTO substrate did
majority of carriers and CuO is a p-type semiconductor with holes as the not show any light response in the system (Fig. S12). In addition, ZnO
carrier majority. In order to further verify the existence of the p-n and CuO electrodes were used as the air electrodes of rechargeable Zn-
junctions, we perform the M-S analysis at an AC frequency of 1000 Hz in air batteries (Fig. S13, Fig. S14). The ZnO air electrode only showed an
the dark. The p–n junction feature was detected, as shown in the Fig. 4e, enhanced charge activity, while the CuO electrode only promoted the
where the co-existence of positive and negative slopes with similar discharging process. The test results prove that the heterostructure of
values represents the presence of the p–n junction [37]. In order to study ZnO and CuO composite successfully combines the excellent charge
the mechanism of the ZnO/CuO photoelectrode in the light-induced performance of ZnO and discharge performance of CuO, demonstrating
OER and ORR process, a linear sweep voltammetry (LSV) test was car­ their bifunctional characteristics. The long-term stability and efficiency
ried out in the dark and under AM 1.5G simulated sunlight at 100 mW of the batteries were evaluated by continuously repeated cycles with
cm-2. The potential corresponding to the current density of 0.1 mA cm-2 total 220 cycles of testing through 6 min as a charging cycle. In the first
was considered as the starting potential. According to Fig. 4f and 4 g, the circle, the battery displays the discharge and charge potentials of 0.67

7
D. Bu et al. Chemical Engineering Journal 433 (2022) 133559

Fig. 6. Heterostructure charge transfer and Cu’s self-valence mechanism. (a) The mechanism of Cu’s self-valence mechanism during charge and discharge. (b) XRD
patterns of new CuO film on FTO. (c) XRD patterns of Cu2O film after discharging on FTO. (d) XRD patterns of CuO film after discharging and charging cycle on FTO.
(e) The charge mechanism of Zn-air battery based on sunlight promotion strategy. (f) The discharge mechanism of Zn-air battery based on sunlight promo­
tion strategy.

and 2.02 V, respectively, indicating that the voltage gap (Δη) is 1.35 V. we conducted a long-term charging and discharging tests on the CuO
When the reaction proceeds to the 30th h, the voltage gap (Δη) increased semiconductor electrode to further verify the process and observed the
to 1.8 V (Fig. S15). Such phenomenon likely arises from an irreversible surface color change on the CuO electrode. As illustrated in Fig. 6a, the
Zn plating-stripping process[15]. In the test under simulated light, 220 surface of the black CuO film electrode turned dark red in the long-term
test cycles were completed in four time periods under the same ZnO/ discharging process, and then it turned black again in the subsequent
CuO photoelectrode and electrolyte, considering the working time of the charging process. Furthermore, it can be seen from the XRD patterns
xenon lamp is limited. Fig. 5h shows a highly stable discharge voltage before and after the electrode reaction (Fig. 6b and 6d) that the strong
over the 22 h test. The charge voltage fluctuates slightly during this diffraction peaks of the CuO film at the beginning of and after the
period, but the good connection of charge and discharge voltage under charging and discharging cycle appears at 35.5◦ and 38.7◦ , which
the time interval state fully reflects the excellent photocatalytic activity correspond to the crystal planes of (002) and (111) orientations of the
and stability of ZnO/CuO. The electrochemical performance of the ZnO/ CuO (JCPDS 45-0937). The diffraction peaks of the dark red sample,
CuO photoelectrode was further studied using the Electrochemical which can readily be indexed to the standard card of Cu2O (JCPDS 05-
impedance spectroscopy (EIS) test (Fig. S16). The electrode spectrum 0667), were formed during the long-term discharging process while
shows a semicircular shape. Under simulated lighting conditions, the no impurity peak was observed. The XRD patterns and insignificant
radius of the EIS curve was reduced, indicating that the load transfer color changes of ZnO/Cu2O and ZnO/CuO electrodes after the charging
resistance is reduced and thus reducing the impedance of the entire and discharging further confirm that the valence change of CuO (the
battery due to the conductivity of the electrode reaction. conversion between CuO and Cu2O) is an important reason for the dual
During the charging and discharging experiment, we observed that functions of the electrode (Fig S17, Fig. S18, Fig S19).
the electrode has a discoloration phenomenon, which indicates that the In order to further study the charge transfer mechanism during the
valence change of CuO (the conversion between CuO and Cu2O) may be charging and discharging processes, the band positions and redox po­
an important reason for the dual functions of the electrode. Therefore, tentials in the whole system are built. The optical characteristics of Cu2O

8
D. Bu et al. Chemical Engineering Journal 433 (2022) 133559

Fig. 7. (a) Detailed view of the photo-assisted Zn-air battery. (b) The practical application of lighting up the LEDs

were investigated using UV–vis reflectance spectroscopy and converted discharging process Zn-air batteries originates from the valence mech­
into a Tauc’s plots to characterize its band gap width (Fig. S20). anism of Cu, which leads to the formation of ZnO/CuO and ZnO/Cu2O
Meanwhile, the M-S curve of the Cu2O film (Fig. S21) and the cyclic heterostructures.
voltammetry of Cu2O electrode (Fig. S22) were also tested. The results The self-made battery device and its structure diagram are shown in
also show that the Cu2O is a p-type semiconductor with a band gap of 2 Fig. 7. The internal separators and baffles of the battery are used to fix
eV and a flat band potential of 0.87 eV; and the redox potential of Cu+/ the electrodes to prevent short circuits caused by the electrode contact.
Cu2+ was − 0.2 V (vs. Ag/AgCl). According to previous studies[38], the The slit is tightly integrated with the quartz plate, and the glass glue is
CB level positions (Ec) of Cu2O is − 0.9 V, ZnO is (vs. Ag/AgCl). The used for further sealing during the process. The quartz window is used to
energy band gaps are confirmed based on the data of their UV–vis ensure the transmission of the light. According to Fig. 7b, By connecting
reflectance spectroscopy. The energy band diagram is shown in Fig. S23. three assembled battery devices in series, 7 small LED bulbs connected
According to Fig. S23 and Fig. 4f and 4 g, the relative positions of the in parallel can be lighted. In simulated sunlight conditions, the bright­
semiconductors and redox potentials can be calibrated in the same co­ ness of the LED bulb significantly improved. Fig. S24 shows the 3D
ordinate system to discuss the chrage transfer mechanism. printer is printing the device. The portability of self-made devices and
Fig. 6e and 6f show the charge transfer mechanism during the the photocatalytic activity of electrode materials further enhance the
charging and discharging processes of the Zn-air battery under illumi­ practical application value.
nation, respectively. During the charging process (Fig. 6e), the semi­
conductor air electrode is excited by light to generate photogenerated 4. Conclusion
electrons and holes. During this period, the air electrode collects pho­
tons and drives holes with oxidizing properties to participate in the OER. In summary, the bifunctional ZnO/CuO electrode materials with
The charge transfer mechanism is similar to the type-II heterostructure. excellent photoelectrochemical activity and stability have been
The electrons are transferred from higher (more negative) CB level of designed. The construction of heterostructure promotes the separation
Cu2O to lower (negative) CB level of ZnO, and finally transferred to the and transport of photogenerated holes and electrons, and reduces the
metal electrode through the external circuit to participate in the corre­ probability of charge recombination. Through the introduction of sun­
sponding Zn2+ reduction reaction. A part of the photogenerated holes light promotion strategy, a method of in-situ conversion of energy from
produced by ZnO are directly contacted with the electrolyte and solar energy to electric energy inside the battery is demonstrated. The
participate in the OER (SPV has proven that positive charges have single-electrode Zn-air battery obtains an unprecedented low charge
accumulated on the ZnO surface). Another part of the holes at the ZnO/ voltage of 1.5 V and a high discharge voltage of 1.28 V, which greatly
Cu2O interface can be transferred from lower (more positive) VB level of improve the efficiency of constant current charge and discharge. The
ZnO to higher VB level of Cu2O. Since the potential of the self-oxidation PCE of light-induced discharge is 0.055% (at a current density of 0.1 mA
reaction of Cu+ to Cu2+ is close to the oxidation potential of OH- to O2, cm-2). We revealed that the high-efficiency discharge performance
the holes in Cu2O can be divided into two parts to participate in the originates from the valence mechanism of Cu. The Cu-based materials
above two reactions (Cu+/Cu2+, OER); and in this way, a CuO/ZnO have excellent ORR characteristics. In this work, the effect of the energy
heterostructure that participates in the discharge reaction is formed. The band structure of semiconductors on the charge and discharge perfor­
obvious step change of the charge and discharge curve illustrates the mance of Zn-air battery is carefully and systematically investigated. The
brittleness of the transition from the ZnO/Cu2O heterostructure to the proposed new concept of heterojunction reconstruction due to the self-
ZnO/CuO heterostructure (Fig. 5g). The OER/ORR reaction is guaran­ oxidation-reduction reaction of the catalyst opens up a new avenue for
teed to quickly construct a charge transfer path between hetero­ the novel design of copper-based composite electrode materials, while
structures. During the discharging process, the transfer path of reducing also promoting the application of catalysts based on this concept in other
electrons and the process involved in the reaction are similar to the light-assisted rechargeable metal-air batteries.
above process of holes (Fig. 6f). The photogenerated electrons of ZnO
can be transferred to the CB of CuO. The photogenerated electrons of
CuO can participate in two reactions (Cu2+/Cu+, ORR). All photo- Declaration of Competing Interest
generated holes can be collected at the FTO electrode because the
composite shows a p-type characteristic as a whole (according to the The authors declare that they have no known competing financial
transient results). Thus, our previous conclusion is further verified: the interests or personal relationships that could have appeared to influence
bifunctional catalytic properties in the photo-assisted charging and the work reported in this paper.

9
D. Bu et al. Chemical Engineering Journal 433 (2022) 133559

Acknowledgements [16] S. Li, X. Hao, A. Abudula, G. Guan, Nanostructured Co-based bifunctional

electrocatalysts for energy conversion and storage: current status and perspectives,
J. Mater. Chem. A 7 (32) (2019) 18674–18707.
This work was supported by the National Natural Science Foundation [17] M. Yu, X. Ren, L. Ma, Y. Wu, Integrating a redox-coupled dye-sensitized
of China (No.51773085, 52071171, 21902067), the Natural Science photoelectrode into a lithium-oxygen battery for photoassisted charging, Nat
Fund of Liaoning University (LDGY2019016), Liaoning Revitalization Commun 5 (2014) 5111.
[18] K. Wang, Z. Mo, S. Tang, M. Li, H. Yang, B. Long, Y.i. Wang, S. Song, Y. Tong,
Talents Program - Pan Deng Scholars (XLYC1802005), Liaoning Bai­ Photo-enhanced Zn–air batteries with simultaneous highly efficient in situ H2O2
QianWan Talents Program (LNBQW2018B0048), Natural Science Fund generation for wastewater treatment, J. Mater. Chem. A 7 (23) (2019)
of Liaoning Province for Excellent Young Scholars (2019-YQ-04), Key 14129–14135.
[19] D. Du, S. Zhao, Z. Zhu, F. Li, J. Chen, Photo-excited oxygen reduction and oxygen
Project of Scientific Research of the Education Department of Liaoning evolution reactions enable a high-performance zn-air battery, Angew Chem Int Ed
Province (LZD201902), Australian Research Council (ARC) Future Engl 59 (41) (2020) 18140–18144.
Fellowship (FT210100298), CSIRO Energy Centre Kick-Start Program, [20] J. Lv, S.C. Abbas, Y. Huang, Q. Liu, M. Wu, Y. Wang, L. Dai, A photo-responsive
bifunctional electrocatalyst for oxygen reduction and evolution reactions, Nano
and Victorian Government’s support through the provision of a grant Energy 43 (2018) 130–137.
from veski – Study Melbourne Research Partnerships (SMRP) project. [21] B. Kolodziejczyk, O. Winther-Jensen, D.R. MacFarlane, B. Winther-Jensen,
Conducting polymer alloys for photo-enhanced electro-catalytic oxygen reduction,
J. Mater. Chem. 22 (21) (2012) 10821, https://doi.org/10.1039/c2jm30992k.
Appendix A. Supplementary data [22] B. Qian, Q. Xu, Y. Wu, Y. Zhang, H. Li, Y. Wang, B. Wang, S. Li, X.-M. Song,
A highly efficient photocatalytic methanol fuel cell based on non-noble metal
Supplementary data to this article can be found online at https://doi. photoelectrodes: Study on its energy band engineering via experimental and
density functional theory method, J. Power Sources 478 (2020).
org/10.1016/j.cej.2021.133559.
[23] C.Y. Toe, Z. Zheng, H. Wu, J. Scott, R. Amal, Y.H. Ng, Photocorrosion of Cuprous
Oxide in Hydrogen Production: Rationalising Self-Oxidation or Self-Reduction,
References Angew Chem Int Ed Engl 57 (41) (2018) 13613–13617.
[24] J. Liu, J. Ke, D. Li, H. Sun, P. Liang, X. Duan, W. Tian, M.O. Tade, S. Liu, S. Wang,
[1] Y. Zhang, W. Sun, B. Qian, Y. Wang, B. Wang, S. Li, D. Liu, D. Feng, T. Ma, X.- Oxygen vacancies in shape controlled Cu2O/reduced graphene oxide/In2O3 hybrid
M. Song, Room-temperature photocatalytic methanol fuel cell based on one- for promoted photocatalytic water oxidation and degradation of environmental
dimension semiconductor photoanode: Intrinsic mechanism of photogenerated pollutants, ACS Appl. Mater. Interfaces 10 (2017) 98–104.
charge separation, Electrochim. Acta 318 (2019) 413–421. [25] Y. Qian, Y. Duan, S. Che, Chiral nanostructured cuo films with multiple optical
[2] K. Qu, Y. Zheng, Y. Jiao, X. Zhang, S. Dai, S.-Z. Qiao, Polydopamine-Inspired, Dual activities, Adv. Opt. Mater. 5 (16) (2017) 1601013, https://doi.org/10.1002/
Heteroatom-Doped Carbon Nanotubes for Highly Efficient Overall Water Splitting, adom.v5.1610.1002/adom.201601013.
Adv. Energy Mater. 7 (9) (2017) 1602068, https://doi.org/10.1002/aenm. [26] W.u. Yang, W. Yang, L. Dong, G. Shao, G. Wang, X. Peng, Hierarchical ZnO
v7.910.1002/aenm.201602068. nanorod arrays grown on copper foam as an advanced three-dimensional skeleton
[3] Y. Li, Q. Wu, Y. Chen, R. Zhang, C. Li, K. Zhang, M. Li, Y. Lin, D. Wang, X. Zou, for dendrite-free sodium metal anodes, Nano Energy 80 (2021) 105563, https://
T. Xie, Interface engineering Z-scheme Ti-Fe2O3/In2O3 photoanode for highly doi.org/10.1016/j.nanoen.2020.105563.
efficient photoelectrochemical water splitting, Appl. Catal. B 290 (2021) 120058, [27] X.-M. Song, C. Yuan, Y. Wang, B. Wang, H. Mao, S. Wu, Y. Zhang, ZnO/CuO
https://doi.org/10.1016/j.apcatb.2021.120058. photoelectrode with n-p heterogeneous structure for photoelectrocatalytic
[4] X. Liu, Y. Yuan, J. Liu, B. Liu, X. Chen, J. Ding, X. Han, Y. Deng, C. Zhong, W. Hu, oxidation of formaldehyde, Appl. Surf. Sci. 455 (2018) 181–186.
Utilizing solar energy to improve the oxygen evolution reaction kinetics in zinc-air [28] M.A. Butler, Photoelectrolysis and physical properties of the semiconducting
battery, Nat Commun 10 (2019) 4767. electrode WO2, J. Appl. Phys. 48 (1977) 1914–1920.
[5] S.S. Adam D. Printz, Daniel Rodriquez, Darren J. Lipomi n, Role of molecular [29] M.F. Ehsan, T. He, In situ synthesis of ZnO/ZnTe common cation heterostructure
mixing on the stiffness of polymer:fullerene bulk heterojunction films, Solar Energy and its visible-light photocatalytic reduction of CO2 into CH4, Appl. Catal. B
Materials & Solar Cells. 166–167 (2015) 345–352.
[6] X. Duan, N.a. Pan, C. Sun, K. Zhang, X. Zhu, M. Zhang, L.i. Song, H. Zheng, MOF- [30] Y.X.A.M.A.A. SCHOONEN*, The absolute energy positions of conduction and
derived Co-MOF, O-doped carbon as trifunctional electrocatalysts to enable highly valence bands of selected semiconducting minerals, Am. Mineral. 85 (2000)
efficient Zn–air batteries and water-splitting, J. Energy Chem. 56 (2021) 290–298. 543–556.
[7] X. Wang, J. Sunarso, Q. Lu, Z. Zhou, J. Dai, D. Guan, W. Zhou, Z. Shao, High- [31] T. Jiang, T. Xie, Y. Zhang, L. Chen, L. Peng, H. Li, D. Wang, Photoinduced charge
performance platinum-perovskite composite bifunctional oxygen electrocatalyst transfer in ZnO/Cu(2)O heterostructure films studied by surface photovoltage
for rechargeable Zn–Air battery, Adv. Energy Mater. 10 (5) (2020) 1903271, technique, Phys Chem Chem Phys 12 (2010) 15476–15481.
https://doi.org/10.1002/aenm.v10.510.1002/aenm.201903271. [32] D. Zhang, Y. Wang, Y. Wang, Y. Zhang, X.-M. Song, Fe2O3/NiO photocathode for
[8] T.S. Andrade, M.C. Pereira, P. Lianos, High voltage gain in photo-assisted charging photocatalytic methanol fuel cell: An insight on solar energy conversion, J. Alloy.
of a metal-air battery, J. Electroanal. Chem. 878 (2020) 114559, https://doi.org/ Compd. 815 (2020).
10.1016/j.jelechem.2020.114559. [33] T. Xie, Q. Zhao, L. Peng, Y. Lin, P. Wang, L. Peng, D. Wang*, Size- and orientation-
[9] Y. Sun, X. Liu, Y. Jiang, J. Li, J. Ding, W. Hu, C. Zhong, Recent advances and dependent photovoltaic properties of zno nanorods, J. Phys. Chem. C 111 (2007)
challenges in divalent and multivalent metal electrodes for metal–air batteries, 17136–17145.
J. Mater. Chem. A 7 (31) (2019) 18183–18208. [34] M.R. Nellist, F.A. Laskowski, F. Lin, T.J. Mills, S.W. Boettcher, Semiconductor-
[10] S. Sfaelou, P. Lianos, Photoactivated Fuel Cells (PhotoFuelCells) An alternative electrocatalyst interfaces: theory, experiment, and applications in
source of renewable energy with environmental benefits, AIMS Mater. Sci. 3 photoelectrochemical water splitting, Acc Chem Res 49 (2016) 733–740.
(2016) 270–288. [35] Shan Jiang, Jing Cao, Minna Guo, Dongdong Cao, Xuemei Jia, Haili Lin,
[11] M. Li, Y. Liu, L. Dong, C. Shen, F. Li, M. Huang, C. Ma, B. Yang, X. An, W. Sand, Shifu Chen, Novel S-scheme WO3/RP composite with outstanding overall water
Recent advances on photocatalytic fuel cell for environmental applications—The splitting activity for H2 and O2 evolution under visible light, Appl. Surf. Sci. 558
marriage of photocatalysis and fuel cells, Sci. Total Environ. 668 (2019) 966–978. (2021) 149882, https://doi.org/10.1016/j.apsusc.2021.149882.
[12] B. Zhang, S. Wang, W. Fan, W. Ma, Z. Liang, J. Shi, S. Liao, C. Li, Photoassisted [36] J. Wang, L. Yang, L. Zhang, Constructed 3D hierarchical micro-flowers CoWO4@
Oxygen reduction reaction in H2–O2 fuel cells, Angew. Chem. Int. Ed. 55 (2016) Bi2WO6 Z-scheme heterojunction catalyzer: Two-channel photocatalytic H2O2
14748–14751. production and antibiotics degradation, Chem. Eng. J. 420 (2021).
[13] J. Fu, Z.P. Cano, M.G. Park, A. Yu, M. Fowler, Z. Chen, Electrically rechargeable [37] J. Li, F. Meng, S. Suri, W. Ding, F. Huang, N. Wu, Photoelectrochemical
Zinc-Air batteries: progress, challenges, and perspectives, Adv Mater 29 (2017). performance enhanced by a nickel oxide-hematite p-n junction photoanode, Chem
[14] S. Han, X. Hu, J. Wang, X. Fang, Y. Zhu, Novel route to fe-based cathode as an Commun (Camb) 48 (2012) 8213–8215.
efficient bifunctional catalysts for rechargeable zn-air battery, Adv. Energy Mater. [38] Yanming Wang, Yalin Lan, Degang Bu, Bingzhi Qian, Yang Wang, Baoxin Wang,
8 (22) (2018) 1800955, https://doi.org/10.1002/aenm.v8.2210.1002/ Qiong Wu, Shuo Li, Yu Zhang, Xi-Ming Song, A study on tandem photoanode and
aenm.201800955. photocathode for photocatalytic formaldehyde fuel cell, Electrochim. Acta 352
[15] S. Ren, X. Duan, S. Liang, M. Zhang, H. Zheng, Bifunctional electrocatalysts for (2020) 136476, https://doi.org/10.1016/j.electacta.2020.136476.
Zn–air batteries: recent developments and future perspectives, J. Mater. Chem. A 8
(2020) 6144–6182.

10