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Review

Perovskite Catalysts for Oxygen Evolution and Reduction Reactions in Zinc-Air Batteries

by
Zheng Zhu
,
Qiangqiang Song
,
Baokai Xia
,
Lili Jiang
,
Jingjing Duan
and
Sheng Chen
*
Key Laboratory for Soft Chemistry and Functional Materials (Ministry of Education), School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
*
Author to whom correspondence should be addressed.
Catalysts 2022, 12(12), 1490; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12121490
Submission received: 9 November 2022 / Revised: 18 November 2022 / Accepted: 19 November 2022 / Published: 22 November 2022
(This article belongs to the Special Issue Electrocatalysts for Oxidation-Reduction Reactions)
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Abstract

:
The Zinc-air battery (ZAB) has become a hot research topic for nearly a decade due to its high energy densities. As an important category of catalysts for ZAB, perovskites have attracted extensive interests because of their environmentally friendly properties, cheapness, and excellent electrocatalytic performances. This review article discusses the mechanistic analyses regarding the progress of perovskites for ZAB. In addition, electrode manipulation methods of perovskites for battery device are also emphasized. Finally, perspectives are given on the limitations of the current perovskite catalysts for ZABs. We hope that this review will provide new clues for promoting perovskites as catalysts for many energy-storage and conversion applications in the future.

1. Introduction

The rapid development of new batteries for electrocatalysts needs to meet two requirements of being ecofriendly and providing high energy densities [1,2,3,4,5,6,7]. Recently, zinc-air batteries (ZABs) have become a hot spot for research because of their low-cost, high-energy density, portability, environmental friendliness, and durable charge/discharge cycle effects [8,9,10]. Unlike classic lithium-air battery, catalysts loaded on the positive electrode of ZABs are versatile and the battery is designed and assembled under ambient atmosphere. More importantly, lithium-air batteries usually suffer from fast activity decay because of forming Li2O [11,12], while ZABs could demonstrate strong durability up to hundreds of charging-discharging cycles and reach an ultra-high theoretical energy density of 1300–1400 Wh kg−1 [13].
Principally, the charging-discharging processes of ZAB are based on electrocatalytic oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). The overall charging-discharging processes are listed follows [13,14,15,16,17]:
O2 + 2H2O + 4e− ↔ 4OH−, E = 0.40 V vs. SHE (air electrode reaction)
Zn + 2OH− ↔ ZnO + H2O + 2e−, E = −1.26 V vs. SHE (zinc electrode reaction)
2Zn + O2 ↔ 2ZnO, E = 1.66 V vs. SHE (overall reaction)
In the case of OER, it can be divided into adsorbate evolution mechanism (AEM, which considers the metal site as active site) and lattice oxygen mechanism (LOM, which considers the lattice oxygen in catalysts participate in the OER reaction as well) [18]. The overpotential of OER based on AEM is higher than that of LOM because of the formation of *OOH during LOM, which are subject to the linear relationship between *OH and *OOH [19,20,21,22]. On the other hand, ORR can be classified into 2e− and 4e− transfer processes [13,17,23].
The formation of H2O2 and HO2− needs high overpotentials due to the high energy required for the breakage of the O=O, so the whole ORR process becomes inefficient in two-electron process. Furthermore, these H2O2 and HO2− intermediates can also corrode the catalysts and the carrier, leading to the destruction of catalyst structures and degraded overall performances. Therefore, the reaction process of ORR is closely related to the choice of catalysts, and it is crucial to select a catalyst that boosts the 4e− transfer process [24,25].
Currently, among the catalysts that efficiently drive charging-discharging cycles of ZAB, noble metals and noble metal oxides rank as the benchmarks. Particularly, they possess high conductivities, low overpotentials (RuO2 for OER, ~1.56 V vs. RHE), and ultra-high half-wave potentials (Pt for ORR, ~0.84 V vs. RHE), so they are often used as an important indicator for various electrocatalysts in ZABs [26,27,28,29]. Nevertheless, their expensive price inhibits widespread application. As a result, low-cost alternatives (such as perovskites) show a promising future to replace noble metals for ZABs.
Generally, perovskite oxides are presented in the structural formula of ABO3−δ which has shown the advantages of cheap prices, simple synthesis, controllable morphologies, optimal stability, and durability [30,31,32,33,34]. The A-site ions are usually alkaline/rare earth ions with ionic radius rA > 0.090 nm (like La, Pr, Nd, Ca, Sr, Ba, Ce, etc); and the B-site ions are transition metal ions with ionic radius rB > 0.051 nm (like Fe, Cr, Co, etc.). In a single lattice, the O element and the larger radius A ion together form a cubic compact stack, and B ions are filled in the octahedral gap [35,36,37]. According to their components, perovskites can be divided into single-component perovskites (ABO3−δ), A site substituted perovskites (AA′BO3−δ), B site substituted perovskites (ABB′O3−δ), and perovskites substituted at both the A and B sites (AA′BB′O3−δ) [38,39,40]. Besides, A/B-site cation ordered double perovskites are also included. The A-site cation double perovskites A′A′′B2O5+δ exhibit layered structures with a stacking sequence of [A′Oδ]-[BO2]-[A′′O]-[BO2]-[A′Oδ] along the c axis. All oxygen vacancies are confined to A′O plane because of oxygen migration. B-site cation double perovskite A2B′B′′O6 possesses alternately occupied transition metal sites of B′ and B′′ cations. The formation of B′O6 and B′′O6 octahedra structures have originated from intervening oxygen bridging the B′ and B′′ atom pair that usually impart unique properties to the materials in catalysis (including ZABs) [41,42]. Usually, hetero-valent metal elements are used in place of A/B site ions that can induce defects or change their valences, which can significantly alter the catalytic activities. Moreover, when transition metals of different valence are doped, electron exchange reactions are also generated, which can improve the conductivities of the materials.
At present, there are already many studies on the simultaneous doping of perovskites at A and B sites, and the corresponding catalytic activities of ORR and OER have been significantly enhanced. Some classic examples of perovskites (like Ba0.5Sr0.5Co0.8Fe0.2O3−δ [43] and La0.6Sr0.4CoO3−δ [44]) have already been applied in ZAB. Their ORR and OER activities are comparable to commercial noble materials [45,46,47]. In addition to perovskite materials, there are many other materials that possess high ORR and OER activities and are promising for ZABs. Jiang et al. [48] have prepared Co-N/C+NG catalyst applied to alkaline ORR with an impressive half-wave potential of 0.91 V (vs. RHE). The power density of ZAB prepared by mixing this catalyst with Pt/C+IrO2 for air electrode has reached as high as 430 mW cm−2. In this paper, we review the applications of perovskites in ZABs. As shown in Figure 1, we focus on the modification of perovskite catalysts on air electrodes. We have summarized information on perovskites applied to ZABs in recent years, as detailed in Table 1. The mechanisms for the activity improvement of perovskites for ZABs are also discussed. Further, we will discuss the potential market applications for perovskite based ZABs.

2. Zinc-Air Battery Configuration

As shown in Figure 2a, ZAB consists of the following components: gas diffusion layers, catalyst layers, electrolytes, separators, and zinc electrodes. The critical component of ZABs are constant flows of oxygen gas from air electrodes. Different from the Li-air battery, the ZAB’s Zn electrode is not prone to disturbance upon exposure to air [49]. Besides above components, the conventional planar ZABs also include positive/negative current collectors and numbers of holes in the top of the battery that closely contact with air [50,51]. However, there is a high possibility of electrolyte evaporation due to the presence of air contact holes, which leads to a significant limitation in the efficiency of ion flow between the air and zinc electrodes [52,53]. Later, the emergence of flow-type ZABs provide a good solution to above problem. The major architecture of flow-type ZABs is the same as conventional planar batteries, but their electrolyte is designed to flow in a circular form [54,55]. Consequently, the flowing electrolyte can allow for ion flowing between these two electrodes. Further, the flowing electrolyte is also useful for mitigating the problem of dendrite formation at the zinc electrode, thus avoiding battery performance decay.
Very recently, flexible-type batteries have become the mainstream for electrochemical applications [56]. ZAB is a good choice for adapted into flexible battery for their outstanding safety, high energy density, and cheapness. However, to design flexible-type ZABs, solid electrolytes need to be developed to replace traditional electrolytes, and electrodes and battery devices need to be designed with sufficient mechanical strength and bending degree of materials [57,58,59,60]. Therefore, there is still a long way to go before ZAB can be widely used in the market.
In addition, the loss and corrosion of ZAB anode metal zinc has been one of the main reasons for the poor battery life [61,62]. Recent studies have shown several strategies of adding surfactants, carbon materials to the surface of zinc metal, or mixing with other metal materials to make electrodes, which can effectively reduce the loss of anode and elongate the battery life [62]. On the other hand, since ZAB anodes have been built into porous structures, the use of 3D conductive host materials and the method of inhibition can also effectively alleviate above problems (Figure 2b) [17]. Further, when the battery is charged (OER process), the anode Zn metal will bulge to become Zn dendrite; when the battery is discharged (ORR process), the metal Zn will become ionic state and react with O2 to form ZnO [63,64,65]. Therefore, the consumption of anode Zn cannot be fully avoided. Meanwhile, conventional ZAB anode undergoes the sluggish kinetic process of ORR, and OER leads to high charge/discharge voltage difference, which greatly limits the energy efficiency and lifetime of the battery [66,67,68,69]. To solve this problem, Zhang et al. [70] designed a Zn-Cu/Ni/air hybrid battery, which was different from traditional ZAB (Figure 2c). Herein, the ORR, OER reaction at the cathode of the battery is accompanied by reversible redox reactions of Cu+/Cu2+ and Ni2+/Ni3+, which can generate additional high discharge voltage plateaus and low charge voltage plateaus, thus improving the efficiency of the battery.
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Figure 2. (a) Schematic charging and discharging processes of zinc-air batteries; (b) up: methods to decrease Zn dendrite growth and undesired relocation: employing a high surface area porous Zn structure; confining Zn in 3D conductive host materials; inhibition/suppression; down: mechanism of anode Zn deactivation during the ZAB charge/discharge cycle [17]. Copyright 2018, Wiley-VCH; (c) comparison of electrochemical mechanisms and scheme of Zn-Cu/Ni/air hybrid battery [70]. Copyright 2022, American Chemical Society.
Figure 2. (a) Schematic charging and discharging processes of zinc-air batteries; (b) up: methods to decrease Zn dendrite growth and undesired relocation: employing a high surface area porous Zn structure; confining Zn in 3D conductive host materials; inhibition/suppression; down: mechanism of anode Zn deactivation during the ZAB charge/discharge cycle [17]. Copyright 2018, Wiley-VCH; (c) comparison of electrochemical mechanisms and scheme of Zn-Cu/Ni/air hybrid battery [70]. Copyright 2022, American Chemical Society.
Catalysts 12 01490 g002

3. Perovskite Manipulation for Zinc-Air Batteries

3.1. Morphology Control of Perovskites

Morphology control can enhance catalysts’ activities [71,72,73,74]. Common morphologies used for OER/ORR are nanofibers, nanoparticles, hollow structures, core-shell structures, etc. [75,76]. For instance, Kim et al. [77] designed a novel heterojunction oxygen catalyst (PrBa0.5Sr0.5)0.95Co1.5Fe0.5O5+δ (PBSCF)/3D porous N-doped graphene (P-3G). The insertion of 3DNG into PBSCF nanofibers by coaxial electrospinning (Figure 3a) and the accompanying synergistic effect of this A-site defect of PBSCF greatly enhanced the ORR and OER activities of pristine PBSCF. Due to the introduction of 3DNG, the d-band centers of Co and Fe in the pristine PBSCF are brought close together (Figure 3b). This makes P-3G high ORR half-wave potential (0.82 V vs. RHE) and low OER overpotential (1.56 V vs. RHE) (Figure 3c,d). The ZAB with a P-3G catalyst coated on the surface of the gas diffusion layer showed a peak power density of 128.5 mW cm−2 and could operate for more than 50,000 s (110 cycles) at a current density of 10 mA cm−2 (Figure 3e,f).
Without carbon materials, single perovskite-based electrocatalysts also exhibit excellent activities for ORR and OER [78,79]. Further, the calcination temperature is one of the most important factors to determine the properties of perovskites [80,81]. For example, the La0.8Sr0.2Co0.4Mn0.6O3−δ (LSCM) with larger nanoparticles (Figure 4b) synthesized by a sol-gel mothed exhibited an outstanding ORR activity [82]. The author selected La element as one of the perovskite A-site elements because the phase formation temperature in the presence of La element is lower compared to PrBa-based and BaSr-based perovskite oxides. The lower phase formation temperature allows the perovskite oxides to retain high specific surface areas for electrocatalytic reactions. Consequently, the La0.8Sr0.2Co0.4Mn0.6O3−δ possesses an ORR half-wave potential of 0.7 V vs. RHE and an OER overpotential of 1.73 V vs. RHE (Figure 4a). The power density of the ZAB cathode loaded with this catalyst reached 160 mW cm−2. At a current density of 10 mA cm−2, the battery showed a small increase of the voltage gap (approximately 0.18 V vs. Zn) after 16 h of charge/discharge cycles.
It is found that the specific surface area of most perovskite nanoparticle catalysts prepared by sol-gel method is very low (~20 m2 g−1) [83,84]. To increase the specific surface areas, Emiliana Fabbri et al. [85] used flame spray (FS) method to synthesize highly porous structures Ba0.5Sr0.5Co0.8Fe0.2O3−δ powders composed of fairly monodisperse nanoparticles within the range of 5–15 nm (Figure 4c). In addition, the Co ion valence in the Ba0.5Sr0.5Co0.8Fe0.2O3−δ synthesized by the FS method is lower than that in the Ba0.5Sr0.5Co0.8Fe0.2O3−δ synthesized by the conventional sol-gel method with the same ratio [85,86]. Consequently, Ba0.5Sr0.5Co0.8Fe0.2O3−δ nanoparticles synthesized by FS method possesses a breakthrough kinetics compared to conventional Ba0.5Sr0.5Co0.8Fe0.2O3−δ. Further, the author used operando XAS tests to analyze the mechanism. When the applied potential of anode increased from 1.2 to above 1.425 V, the Co K-edge underwent a trend from no change to shifted to higher energies (Figure 4g). The degree of increase in the oxidation state of Co and local atomic structure changes affect the catalyst OER activity. As seen in Figure 4d, by comparing BSCF with CoO, the author found that the Ba0.5Sr0.5Co0.8Fe0.2O3−δ Co K-edge showed a decreasing trend, while the CoO Co K-edge showed an insignificant decreasing trend. Therefore, it is easy to find from Figure 4d–f that BSCF has the most significant variation in both Co K-edge XANES spectra and FT-EXAFS spectra, and BSCF possessed the smallest Tafel slope. These phenomena indicated that the Ba0.5Sr0.5Co0.8Fe0.2O3−δ synthesized by the FS method possessed the fast OER kinetics.
Catalysts 12 01490 g004 550
Figure 4. (a) ORR and OER polarization curves of LSCM; (b) TEM and HRTEM images of LSCM [82]. Copyright 2017, Elsevier Ltd.; (c) TEM and HRTEM images of BSCF; (d) XANES spectra recorded at the Co K-edge; (e) Tafel plots; (f) Fourier-transform (FT) of the k3-weighted EXAFS records; (g) Current and shift of the Co K-edge position records; (h) OER/LOER and dissolution/re-deposition mechanism [85]. Copyright 2017, Macmillan Publishers Limited.
Figure 4. (a) ORR and OER polarization curves of LSCM; (b) TEM and HRTEM images of LSCM [82]. Copyright 2017, Elsevier Ltd.; (c) TEM and HRTEM images of BSCF; (d) XANES spectra recorded at the Co K-edge; (e) Tafel plots; (f) Fourier-transform (FT) of the k3-weighted EXAFS records; (g) Current and shift of the Co K-edge position records; (h) OER/LOER and dissolution/re-deposition mechanism [85]. Copyright 2017, Macmillan Publishers Limited.
Catalysts 12 01490 g004
Based on above analyses, the authors have proposed OER and LOER mechanisms for Ba0.5Sr0.5Co0.8Fe0.2O3−δ as follows (Figure 4h):
2OH−aq ↔ (1/2)O2 + H2O + 2e−
ABO3−δ + OH− ↔ BO(OH) + A2+aq + [(2 − δ)/2]O2 + 3e−
The Co/Fe oxy (hydroxide) layer is formed due to LOER [22,85]. The A-site ions in Perovskite oxides dissolved within the electrolyte and diffused across the electrode. However, the B-site ions have limited dissolution, allowing for deposition on the oxy (hydroxide) layer. Moreover, the partial dissolution of B-site ions led to a faster deposition on the oxy (hydroxide) layer at the electrode. This could contribute to the stability of this class of perovskite oxygen electrocatalysts. Therefore, although the author did not apply the Ba0.5Sr0.5Co0.8Fe0.2O3−δ synthesized by FS method to ZAB, the mechanism and material’s surface kinetics modulation behind it had a profound influence on the search for suitable perovskite oxygen electrocatalysts for application in ZAB charging reaction. Besides, the enhancement of specific surface area and the deeper study of kinetics also provide good reference suggestions for the improvement of perovskite oxide ORR behavior.

3.2. Defect Engineering of Perovskites

For perovskites, the presence of defects in the A, B, and O sites affect the charge distribution, spin transitions, and band structure [87,88,89]. The electrocatalytic activities of perovskite oxygen electrocatalysts can often be improved by tuning the chemical properties of internal and surface defects [78,90,91].
For instance, Jung et al. [92] prepared Ba0.5Sr0.5Co0.2Fe0.8O3−δ with a large quantity of oxygen vacancies using a sol-gel method. The results showed that Ba0.5Sr0.5Co0.2Fe0.8O3−δ oxygen catalyst exhibited good activities, with an ORR half-wave potential of 0.63 V vs. RHE and an OER overpotential of 1.75 V vs. RHE. Consequently, the author proposed the concept of amorphous layers for performance enhancement, which were formed by heat-treatment at 950 °C for 24 h in argon atmosphere (Figure 5a,b). Due to the presence of Co elements, the amorphous layer on the surface of perovskite thickened when the Co content was high, which led to the decrease of ORR and OER activities. Therefore, the shaping of amorphous layer had a thickness limitation. From Figure 5c,d, the author found from EXAFS tests that the bonding between Ba and O was not linear but distorted due to the influence of structural stresses. The Ba-O bonding was more symmetrical and crystalline after Ar treatment, which led to an increase of oxygen vacancies, due to the abstraction of the O anion adjacent to the Ba cation from the lattice. The part of Co valence state changed to a lower valence state after Ar treatment, which led to a significant reduction in the oxygen anion of the cobalt-oxygen octahedra in perovskite after Ar treatment, resulting in an increase of oxygen vacancies.
Besides oxygen defects, it is theoretically shown that any eg-filling (σ*-orbital occupation) close to 1 of perovskites have the highest ORR activities [93,94]. The structural/chemical flexibilities and high oxygen nonstoichiometry (δ) can not only maintain the cubic symmetry of crystal structure, but also allow it to be applied as a bifunctional oxide electrocatalyst in the Zinc-air battery [90,95,96,97,98]. Consequently, Ba0.5Sr0.5Co0.8Fe0.2O3−δ nanofibers (Figure 5e) were synthesized by electrospinning method [99]. In their work, the author designed A-site defect and oxygen vacancy to enhance the electrochemical performance and applied it in ZAB. The A-site defect introduced more active sites and accelerated charge transport, thus creating a substantial increase in oxygen vacancies. The two synergistic effects further enhanced the Co3+/Co2+ ratio and increased the O22−/O− concentration in this oxygen catalyst (Figure 5f,g). Most critically, this work focused on charge redistribution by means of defects, leading to improved electrochemical and ZAB performances. The battery had a power density of 193.1 mW cm−2, a discharge capacitance of 719.1 mAh g−1 (1.25 V, 10 mA cm−2), and nearly no decay for the aqueous ZABs and flexible ZABs after 140 cycles and 100 cycles, respectively (Figure 5h–j).
Catalysts 12 01490 g005 550
Figure 5. (a,b) TEM and STEM images of Ba0.5Sr0.5Co0.2Fe0.8O3−δ; (c,d) Co, Ba K-edge EXAFS spectra [92]. Copyright 2015, Wiley-VCH; (e) TEM image of Ba0.5Sr0.5Co0.2Fe0.8O3−δ; (f,g) XPS O 1s and Co 2p regions; (h) power density; (i,j) the stability of aqueous ZABs and flexible ZABs [99]. Copyright 2020, Elsevier B.V.
Figure 5. (a,b) TEM and STEM images of Ba0.5Sr0.5Co0.2Fe0.8O3−δ; (c,d) Co, Ba K-edge EXAFS spectra [92]. Copyright 2015, Wiley-VCH; (e) TEM image of Ba0.5Sr0.5Co0.2Fe0.8O3−δ; (f,g) XPS O 1s and Co 2p regions; (h) power density; (i,j) the stability of aqueous ZABs and flexible ZABs [99]. Copyright 2020, Elsevier B.V.
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Guided by the above principle, another Pt@Sr (Co0.8Fe0.2)0.95P0.05O3−δ composite catalyst was constructed [2]. XANES and EXAFS results exhibited that the fast electron transfer of Pt-O-Co bonds and the strong electronic interactions between Pt and SCFP induced by the high concentration of surface oxygen vacancies were the key to the performance increase. Moreover, the spillover effect between noble metals and perovskite oxides can significantly reduce the oxygen catalyst surface energy barrier and change the kinetic rate step, thus enhancing performance.

3.3. Anion/Cation Doping of Perovskites

Elemental doping of perovskites can create defective structures, increase the conductivity of catalysts, and even undergo phase transitions [100,101,102,103]. The common dopants are classified into metallic and non-metallic elements, such as transition metals, sulfur, phosphorus, rare earth/alkaline earth metals, etc. [100,101,102,103,104,105,106]. These anion/cation doping can promote the ORR and OER activities significantly [105,106].
Anion-doped perovskite can cause changes in the electronic structure energy and surface properties of the parent perovskite oxide, thus promoting oxygen catalytic activities [105,106,107]. For instance, Gao’s group reported that sulfur doped LaCoO3 can change the spin state of Co from low spin to intermediate spin and improve the conductivity and substantially enhance the ORR and OER performance [106]. In their work, in addition to the change of Co spin state committed to the enhancement of oxygen catalytic activity, the doping of anionic sulfur also makes the parent perovskite increase the oxygen vacancy concentration, which also contributes to the activity enhancement. Both XPS and XAS results show that the electronic structure energy of Co changes after sulfur doping of LaCoO3 (Figure 6a–c), and the parent perovskite undergoes lattice distortion (Figure 6d). Thus, the power density of the ZAB loaded with this catalyst at the electrode reached 92 mW cm−2, and the aqueous ZABs and flexible ZABs were able to cycle for 100 h and 16 h without degradation, respectively (Figure 6e–g).
On the other hand, it is commonly believed that the A-site elements of perovskite controls the structural stability and plays a role in regulating the valence of the B-site elements, which then influence the overall catalytic activities of perovskites [38,40]. However, some recent studies have demonstrated that the A-site ions can also directly affect the catalytic activities of perovskites, which is related to the radius of the A-site ions and the electronegativity of the electron configuration. Therefore, doping the A-site of the parent perovskite with rare earth/alkaline earth metal cations can promote the catalytic activity [105,108,109,110]. For example, Zeng et al. [105] used Sr and P co-doped LaTiO3 perovskites, which constitute a good electron transport interface with CNT, thus promoting oxygen catalytic activity. The ZAB loaded with this catalyst can be charged/discharged for 180 cycles. Besides, the doping modification of the A-site of such Co-based conventional perovskite oxides as LaMnO3, LaCoO3, etc. for ZAB applications is reported abundantly. Shao-Horn’s group designed an A-site La-doped Lax (Ba0.5Sr0.5)1-xCo0.8Fe0.2O3−δ (LBSCF) perovskite catalyst applied to ZAB, and its charge/discharge performance exceeded that of the commercial catalyst Pt/C [111]. As La is doped into the parent perovskite, La cations occupy Ba or Sr lattice sites and cause oxidation of Co or Fe ions, resulting in a higher valence state. This occurred preferentially in the co-octahedral sublattice (Figure 7a–c). The results of XANES showed that the Co K-edge XANES edge shifted toward the high-energy region, while the Fe K-edge did not change (Figure 7d). This indicated that the preferential oxidation of Co sublattice octahedra increased by La ratio. Furthermore, the EXAFS results showed that at low temperatures, the sublattice of chalcocite was in the same phase; while at high temperatures, Co-O-Fe cation ordering (short Co-O, long Fe-O) or separation of the co-rich phase began to form in the perovskite structure (Figure 7e). These fully demonstrate the effect of doping on the structural changes of perovskite and become crucial for promoting the ORR and OER activities.
As we know, the electronegativity difference of B-O dominates the performance of perovskite oxide (ABO3−δ). Therefore, the selection of a suitable transition metal element cation for doping the B site is crucial [38,40]. Namely, for AB1−x (Bx’)O3−δ (B′ refers to the cationic dopant), the doping of a suitable cation B′ into the parent perovskite oxide ABO3−δ can promote oxygen catalytic activity: the d-band of B and B′ are closer together (a common example, e.g., Co-Fe); the adsorption capacity of the B-O-B′ bond for oxygen is enhanced compared to the original B-O-B bond; the doping of B′ into the parent perovskite increases the concentration of oxygen vacancies, leading to an increase in high surface reactive oxygen species; and causes a phase transition leading to a qualitative change in the catalytic activity of the material.
For instance, Gao et al. [112] doped transition metal W in La0.5Sr0.5CoO3−δ, which led to a significant increase of oxygen catalysis activity. W doping not only effectively optimized the electronic structure of the parent perovskite, but also reduced the number of electrons in the eg orbital, bringing the O 2p-band closer to the Femi level. The power density of ZAB loaded with this catalyst reached 121.23 mW cm−2, and it could be stably charged/discharged for more than 1000 cycles. For another example, Kim et al. [113] enhanced the oxygen catalysis activities of the parent perovskite NdBa0.75Ca0.25Co2O5+δ by trying different transition metal ions (Mn2+, Cu2+, Fe2+ and Ni2+) doped. The results show that Fe2+ B-site doping of NdBa0.75Ca0.25Co2O5+δ possesses the highest ORR and OER activity.
In addition to morphology control, defect engineering, and doping, there are some more methods to modify perovskite materials, e.g., combining perovskites with other materials to enhance the electrocatalytic performances and battery performances. Yang’s group [114] compounded LaMnO3 perovskite with carbon black and Co3O4 by ball milling, and the ORR activity of this composite sample was significantly enhanced. These works can bring perovskites closer to market applications.
Overall, the recently reported perovskites for ZABs are shown in Table 1.
Table
Table 1. Comparison of the performances of ZAB based on perovskite oxide catalysts.
Table 1. Comparison of the performances of ZAB based on perovskite oxide catalysts.
Cathode CatalystSynthesis MethodPower DensityStabilityRef.
La0.8Sr0.2Co0.4Mn0.6O3Sol-gel162 mW cm−2100 cycles[80]
(PrBa0.5Sr0.5)0.95Co1.5Fe0.5O5+δ/N-doped grapheneCoaxial electrospinning128.5 mW cm−2110 cycles[75]
S-doped LaCoO3Sol-gel92 mW cm−2100 h[104]
La0.6Sr0.4TiO3-P@CNTsSol-gel and CVD34 mW cm−2186 cycles[103]
La0.6Sr0.4CoO3−δ/NiFe LDHPechini/100 cycles[43]
Pt-Sr(Co0.8Fe0.2)0.95P0.05O3−δ/C-12Solid-state ball milling122 mW cm−280 h[2]
LaNiO3/N-doped CNTsHydrothermal and CVD/40 h[115]
PrBa0.5Sr0.5Co1.9Ni0.1O5+δSol-gel/20 cycles[116]
La0.7(Ba0.5Sr0.5)0.3Co0.8Fe0.2O3−δPolymerized complex/100 cycles[109]
PrBa0.5Sr0.5Co1.5Fe0.5O5+δElectrospinning127 mW cm−2150 cycles[117]
Ba0.6Sr0.4Co0.79Fe0.21O2.67/NiFe LDHSol-gel61.8 mW cm−2100 h[118]
Ag-Sm0.5Sr0.5CoO3−δSol-gel and ultrasonication104.5 mW cm−2110 h[119]
MnO2/La0.7Sr0.3MnO3Solid-liquid phase reaction181.4 mW cm−2100 cycles[120]
S-doped CaMnO3Electrospinning128 mW cm−2120 cycles[121]
LaMn0.75Co0.25O3−δElectrospinning35 mW cm−270 h[122]
La(Co0.71Ni0.25)0.96O3−δElectrospinning/20 cycles[123]
(La0.8Sr0.2)0.95Mn0.5Fe0.5O3Sol-gel116 mW cm−2100 cycles[124]
LaNi0.85Mg0.15O3Electrospinning45 mW cm−2110 h[125]
CoP-PrBa0.5Sr0.5Co1.5Fe0.5O5+δIn-situ growth138 mW cm−233 h[126]
Ce0.9Gd0.1O2−δ/Pr0.5Ba0.5CoO3−δInfiltration207 mW cm−2200 h[127]
La0.99MnO3.03/CGel auto-combustion430 mW cm−2/[128]
Pr0.5Ba0.5Mn1.7Nb0.1Co0.2O6−δ/LDH-20Sol-gel and hydrothermal65.5 mW cm−2100 h[129]
SrCo0.8Fe0.2O3−δSol-gel106 mW cm−2133 h[130]
La1.7Sr0.3Co0.5Ni0.5O4+δSol-gel60 mW cm−2100 h[131]
La0.5Ca0.5CoO3−δ/rGOAmorphous citrate precursor method, Hummers and ultrasonication225 mW cm−2300 cycles[132]
CaCu3Ti4O12Oxalate precursor method127 mW cm−270 cycles[133]
Sr2TiMnO6Solid-statesynthesis95 mW cm−2500 cycles[134]
Pr0.6Sr0.4Fe0.8Mn0.2O3−δCitrate-nitrate combustion56.3 mW cm−2135 h[135]
2LaCo0.7Fe0.3O3/N-doped carbonSol-gel116 mW cm−224 h[136]
(La0.8Sr0.2)0.95MnO3Sol-gel104 mW cm−2100 cycles[137]

4. Prospective Applications of Perovskite-Based Zinc-Air Batteries

4.1. Electric Vehicles

Nowadays, fuel vehicles have caused fossil energy decay and environmental problems [138,139]. As a result, electric vehicles (EVs) have become an excellent candidate. There is no doubt that Zinc-air batteries will play a central role in electric vehicles. For example, the ZAB recently developed by APET only weighs 180 kg and is capable to generate 44 kWh of power with a range of 350 km. To generate the same amount of power, a lithium-ion battery would have to weigh 360 kg. In terms of cost per unit of electricity, the ZAB is only one-tenth of the lithium-ion battery [49,140,141]. Further, ZAB uses zinc and air to generate electricity directly. After the battery runs out, only the encapsulated zinc powders/rods need to be replaced, which can be done in minutes and is as convenient as refueling. Meanwhile, zinc powders/rods can be sold through existing gas stations, supermarkets, and other channels, while general battery EVs require large-scale construction of “charging stations”. Mechanical rechargeable zinc-air batteries were considered for powering portable military electronics in the 1960s. They have designed self-contained solutions with the addition of zinc pellets and alkaline electrolyte, which helps reduce refueling time to less than 10 min for a 15 kW, 55 kWh battery cell. Israel’s Arotech Co., Ltd. used a mechanically replaceable zinc cartridge [142]. A discarded battery cartridge can be replaced in less than 30 s. The technology was evaluated in a small Jeep where the battery cell used was a module with 32 cells connected in series. The battery cell had a specific energy density of 191 Wh kg−1 and a power density of over 80 W kg−1 [143]. Thus far, an electric bike powered by ZAB is already on the streets of Shanghai City, China, and the best feature of this ZAB vehicle is its long driving range of 200 km.

4.2. Hearing Aids

Hearing aids are as vital to people with hearing loss [59,139,144]. ZAB is the best power source for behind-the-ear, in-the-ear, and canal advanced hearing aids. The following models of ZAB-driven hearing aids have been developed: A675 for behind-the-ear (BTE) hearing aids; A13 for behind-the-ear (BTE) and in-the-ear (ITE) hearing aids; A312 for in-the-ear (ITE) and in-the-canal (ITC) hearing aids; A10 for in-the-canal (ITC), and deep in-the-canal (CIC) hearing aids. In these devices, ZABs can work for a minimum of three days and a maximum of 70 days. This saves a lot of time for recharging. Compared to conventional imported hearing aid internal batteries, the ZAB is much cheaper, reaching only about one third of the price of conventional imported batteries, and since ZAB-driven hearing aids are new products, brands are sure to provide good after-sales service for the sake of their reputation [145,146].

5. Summary and Outlook

In this paper, we review perovskite catalysts and their applications in ZABs. We describe and analyze several strategies of manipulating perovskites, such as morphology control, A/B/O-site defect engineering, and anion/cation doping. In addition to catalyst specific modifications, potential applications for ZABs have also been discussed. Despite fast progress, there is still much room for further breakthroughs in this research field. The specific recommendations are as follows:
(1)
The microscopic changes of perovskite oxides during ORR, OER need further in-depth observation by in situ or operando characterization techniques. It is known that OER/ORR processes are often accompanied by material surface reconfigurations, and the related phenomenon has been observed by a few researchers. However, due to the lack of in situ/operando techniques, many meaningful oxygen catalysis processes on perovskites could not be justified. For example, the detailed mechanism of cation dissolution can be well analyzed if the spherical aberration corrected transmission electron microscope were combined with in situ/operando observation during the charging/discharging process.
(2)
The synthetic and modification strategies of perovskites catalysts need to be scalable. Many scholars test the OER/ORR performances of perovskites in a three-electrode electrolyzer, but they lack satisfactory battery performance once assembled into ZAB. Therefore, catalyst performance tests need to be performed under practical conditions. To further enhance the OER/ORR activities of perovskites, they can be combined with some classical materials, such as graphene and carbon nanotubes, to boost synergistic effects, which could finally lead to ultra-high ZAB performances for practical applications.

Author Contributions

Original draft preparation, Z.Z.; discussion and editing, Q.S., B.X., L.J., J.D. and S.C.; conceptualization, discussion, review and editing, S.C. All authors have read and agreed to the published version of the manuscript.

Funding

The authors would like to acknowledge the financial support from National Natural Science Foundation (Grant No. 92163124, 51888103 and 52006105), Jiangsu Natural Science Foundation (Grant No. BK20190460), and Fundamental Research Funds for the Central Universities (Grant No. 30920041113 and 30921013103).

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Du, D.; Zhao, S.; Zhu, Z.; Li, F.; Chen, J. Photo-Excited Oxygen Reduction and Oxygen Evolution Reactions Enable a High-Performance Zn-Air Battery. Angew. Chem. Int. Ed. 2020, 59, 18140–18144. [Google Scholar] [CrossRef] [PubMed]
  2. Wang, X.; Sunarso, J.; Lu, Q.; Zhou, Z.; Dai, J.; Guan, D.; Zhou, W.; Shao, Z. High-Performance Platinum-Perovskite Composite Bifunctional Oxygen Electrocatalyst for Rechargeable Zn-Air Battery. Adv. Energy Mater. 2020, 10, 1903271. [Google Scholar] [CrossRef]
  3. Yin, J.; Jin, J.; Liu, H.; Huang, B.; Lu, M.; Li, J.; Liu, H.; Zhang, H.; Peng, Y.; Xi, P.; et al. NiCo2O4-Based Nanosheets with Uniform 4 Nm Mesopores for Excellent Zn-Air Battery Performance. Adv. Mater. 2020, 32, 2001651. [Google Scholar] [CrossRef] [PubMed]
  4. Jiang, L.; Xu, S.; Xia, B.; Chen, S.; Zhu, J. Defect Engineering of Graphene Hybrid Catalysts for Oxygen Reduction Reactions. J. Inorg. Mater. 2022, 37, 215–222. [Google Scholar] [CrossRef]
  5. Pan, F.; Li, Z.; Yang, Z.; Ma, Q.; Wang, M.; Wang, H.; Olszta, M.; Wang, G.; Feng, Z.; Du, Y.; et al. Porous FeCo Glassy Alloy as Bifunctional Support for High-Performance Zn-Air Battery. Adv. Energy Mater. 2021, 11, 2002204. [Google Scholar] [CrossRef]
  6. Doan, T.L.L.; Tran, D.T.; Nguyen, D.C.; Kim, D.H.; Kim, N.H.; Lee, J.H. Rational Engineering CoxOy Nanosheets via Phosphorous and Sulfur Dual-Coupling for Enhancing Water Splitting and Zn-Air Battery. Adv. Funct. Mater. 2021, 31, 2007822. [Google Scholar] [CrossRef]
  7. Qi, D.; Liu, Y.; Hu, M.; Peng, X.; Qiu, Y.; Zhang, S.; Liu, W.; Li, H.; Hu, G.; Zhuo, L.; et al. Engineering Atomic Sites via Adjacent Dual-Metal Sub-Nanoclusters for Efficient Oxygen Reduction Reaction and Zn-Air Battery. Small 2020, 16, 2004855. [Google Scholar] [CrossRef]
  8. Rahman, M.A.; Wang, X.; Wen, C. High Energy Density Metal-Air Batteries: A Review. J. Electrochem. Soc. 2013, 160, A1759–A1771. [Google Scholar] [CrossRef]
  9. Ren, X.; Wu, Y. A Low-Overpotential Potassium-Oxygen Battery Based on Potassium Superoxide. J. Am. Chem. Soc. 2013, 135, 2923–2926. [Google Scholar] [CrossRef]
  10. Narayanan, S.R.; Prakash, G.K.S.; Manohar, A.; Yang, B.; Malkhandi, S.; Kindler, A. Materials Challenges and Technical Approaches for Realizing Inexpensive and Robust Iron-Air Batteries for Large-Scale Energy Storage. Solid State Ion. 2012, 216, 105–109. [Google Scholar] [CrossRef]
  11. Kraytsberg, A.; Ein-Eli, Y. Review on Li-Air Batteries—Opportunities, Limitations and Perspective. J. Power Sources 2011, 196, 886–893. [Google Scholar] [CrossRef]
  12. Shao, Y.; Ding, F.; Xiao, J.; Zhang, J.; Xu, W.; Park, S.; Zhang, J.G.; Wang, Y.; Liu, J. Making Li-Air Batteries Rechargeable: Material Challenges. Adv. Funct. Mater. 2013, 23, 987–1004. [Google Scholar] [CrossRef]
  13. Fu, J.; Cano, Z.P.; Park, M.G.; Yu, A.; Fowler, M.; Chen, Z. Electrically Rechargeable Zinc-Air Batteries: Progress, Challenges, and Perspectives. Adv. Mater. 2017, 29, 1604685. [Google Scholar] [CrossRef] [PubMed]
  14. Li, Y.; Dai, H. Recent Advances in Zinc-Air Batteries. Chem. Soc. Rev. 2014, 43, 5257–5275. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  15. Zhu, X.; Hu, C.; Amal, R.; Dai, L.; Lu, X. Heteroatom-Doped Carbon Catalysts for Zinc-Air Batteries: Progress, Mechanism, and Opportunities. Energy Environ. Sci. 2020, 13, 4536–4563. [Google Scholar] [CrossRef]
  16. Sun, H.; Xu, X.; Kim, H.; Jung, W.; Zhou, W.; Shao, Z. Electrochemical Water Splitting: Bridging the Gaps between Fundamental Research and Industrial Applications. Energy Environ. Mater. 2022, e12441. [Google Scholar] [CrossRef]
  17. Fu, J.; Liang, R.; Liu, G.; Yu, A.; Bai, Z.; Yang, L.; Chen, Z. Recent Progress in Electrically Rechargeable Zinc-Air Batteries. Adv. Mater. 2019, 31, 1805230. [Google Scholar] [CrossRef]
  18. Grimaud, A.; Diaz-Morales, O.; Han, B.; Hong, W.T.; Lee, Y.L.; Giordano, L.; Stoerzinger, K.A.; Koper, M.T.M.; Shao-Horn, Y. Activating Lattice Oxygen Redox Reactions in Metal Oxides to Catalyse Oxygen Evolution. Nat. Chem. 2017, 9, 457–465. [Google Scholar] [CrossRef]
  19. Dau, H.; Limberg, C.; Reier, T.; Risch, M.; Roggan, S.; Strasser, P. The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis. ChemCatChem 2010, 2, 724–761. [Google Scholar] [CrossRef]
  20. Montoya, J.H.; Seitz, L.C.; Chakthranont, P.; Vojvodic, A.; Jaramillo, T.F.; Nørskov, J.K. Materials for Solar Fuels and Chemicals. Nat. Mater. 2016, 16, 70–81. [Google Scholar] [CrossRef]
  21. Rong, X.; Parolin, J.; Kolpak, A.M. A Fundamental Relationship between Reaction Mechanism and Stability in Metal Oxide Catalysts for Oxygen Evolution. ACS Catal. 2016, 6, 1153–1158. [Google Scholar] [CrossRef]
  22. Man, I.C.; Su, H.Y.; Calle-Vallejo, F.; Hansen, H.A.; Martínez, J.I.; Inoglu, N.G.; Kitchin, J.; Jaramillo, T.F.; Nørskov, J.K.; Rossmeisl, J. Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces. ChemCatChem 2011, 3, 1159–1165. [Google Scholar] [CrossRef]
  23. Borghei, M.; Lehtonen, J.; Liu, L.; Rojas, O.J. Advanced Biomass-Derived Electrocatalysts for the Oxygen Reduction Reaction. Adv. Mater. 2018, 30, 1703691. [Google Scholar] [CrossRef] [PubMed]
  24. Zhang, T.; Wang, H.; Zhang, J.; Ma, J.; Wang, Z.; Liu, J.; Gong, X. Carbon Charge Population and Oxygen Molecular Transport Regulated by Program-Doping for Highly Efficient 4e-ORR. Chem. Eng. J. 2022, 444, 136560. [Google Scholar] [CrossRef]
  25. Zheng, Y.; Xu, X.; Chen, J.; Wang, Q. Surface O2− Regulation on POM Electrocatalyst to Achieve Accurate 2e/4e-ORR Control for H2O2 Production and Zn-Air Battery Assemble. Appl. Catal. B Environ. 2021, 285, 119788. [Google Scholar] [CrossRef]
  26. Wu, J.; Zhang, J.; Peng, Z.; Yang, S.; Wagner, F.T. Truncated Octahedral Pt3Ni ORR Electrocatalysts. J. Am. Chem. Soc. 2010, 132, 4984–4985. [Google Scholar] [CrossRef] [PubMed]
  27. Bhalla, A.S.; Guo, R.; Roy, R. The perovskite structure—A review of its role in ceramic science and technology. Mater. Res. Innov. 2000, 4, 3–26. [Google Scholar] [CrossRef]
  28. Chang, F.; Bai, Z.; Li, M.; Ren, M.; Liu, T.; Yang, L.; Zhong, C.J.; Lu, J. Strain-Modulated Platinum-Palladium Nanowires for Oxygen Reduction Reaction. Nano Lett. 2020, 20, 2416–2422. [Google Scholar] [CrossRef]
  29. Wang, C.; Markovic, N.M.; Stamenkovic, V.R. Advanced Platinum Alloy Electrocatalysts for the Oxygen Reduction Reaction. ACS Catal. 2012, 2, 891–898. [Google Scholar] [CrossRef]
  30. Abe, Y.; Satoh, I.; Saito, T.; Kan, D.; Shimakawa, Y. Oxygen Reduction Reaction Catalytic Activities of Pure Ni-Based Perovskite-Related Structure Oxides. Chem. Mater. 2020, 32, 8694–8699. [Google Scholar] [CrossRef]
  31. Wang, C.; Hou, B.; Wang, X.; Yu, Z.; Luo, D.; Gholizadeh, M.; Fan, X. High-Performance A-Site Deficient Perovskite Electrocatalyst for Rechargeable Zn-Air Battery. Catalysts 2022, 12, 703. [Google Scholar] [CrossRef]
  32. Li, Y.; Zhang, W.; Wu, T.; Zheng, Y.; Chen, J.; Yu, B.; Zhu, J.; Liu, M. Segregation Induced Self-Assembly of Highly Active Perovskite for Rapid Oxygen Reduction Reaction. Adv. Energy Mater. 2018, 8, 1801893. [Google Scholar] [CrossRef]
  33. Xu, X.; Su, C.; Shao, Z. Fundamental Understanding and Application of Ba0.5Sr0.5Co0.8Fe0.2O3−δ Perovskite in Energy Storage and Conversion: Past, Present, and Future. Energy Fuels 2021, 35, 13585–13609. [Google Scholar] [CrossRef]
  34. Sunarso, J.; Torriero, A.A.J.; Zhou, W.; Howlett, P.C.; Forsyth, M. Oxygen Reduction Reaction Activity of La-Based Perovskite Oxides in Alkaline Medium: A Thin-Film Rotating Ring-Disk Electrode Study. J. Phys. Chem. C 2012, 116, 5827–5834. [Google Scholar] [CrossRef]
  35. Grabowska, E. Selected Perovskite Oxides: Characterization, Preparation and Photocatalytic Properties—A Review. Appl. Catal. B Environ. 2016, 186, 97–126. [Google Scholar] [CrossRef]
  36. Sánchez, F.; Ocal, C.; Fontcuberta, J. Tailored Surfaces of Perovskite Oxide Substrates for Conducted Growth of Thin Films. Chem. Soc. Rev. 2014, 43, 2272–2285. [Google Scholar] [CrossRef] [Green Version]
  37. Zhu, Y.; Zhou, W.; Shao, Z. Perovskite/Carbon Composites: Applications in Oxygen Electrocatalysis. Small 2017, 13, 1603793. [Google Scholar] [CrossRef]
  38. Peña, M.A.; Fierro, J.L.G. Chemical Structures and Performance of Perovskite Oxides. Chem. Rev. 2001, 101, 1981–2017. [Google Scholar] [CrossRef] [PubMed]
  39. Arandiyan, H.; Mofarah, S.S.; Sorrell, C.C.; Doustkhah, E.; Sajjadi, B.; Hao, D.; Wang, Y.; Sun, H.; Ni, B.J.; Rezaei, M.; et al. Defect Engineering of Oxide Perovskites for Catalysis and Energy Storage: Synthesis of Chemistry and Materials Science. Chem. Soc. Rev. 2021, 50, 10116–10211. [Google Scholar] [CrossRef]
  40. Sun, C.; Alonso, J.A.; Bian, J. Recent Advances in Perovskite-Type Oxides for Energy Conversion and Storage Applications. Adv. Energy Mater. 2021, 11, 2000459. [Google Scholar] [CrossRef]
  41. Cao, Y.; Liang, J.; Li, X.; Yue, L.; Liu, Q.; Lu, S.; Asiri, A.M.; Hu, J.; Luo, Y.; Sun, X. Recent Advances in Perovskite Oxides as Electrode Materials for Supercapacitors. Chem. Commun. 2021, 57, 2343–2355. [Google Scholar] [CrossRef]
  42. Sun, H.; Song, S.; Xu, X.; Dai, J.; Yu, J.; Zhou, W.; Shao, Z.; Jung, W.C. Recent Progress on Structurally Ordered Materials for Electrocatalysis. Adv. Energy Mater. 2021, 11, 2101937. [Google Scholar] [CrossRef]
  43. Arafat, Y.; Azhar, M.R.; Zhong, Y.; Xu, X.; Tadé, M.O.; Shao, Z. A Porous Nano-Micro-Composite as a High-Performance Bi-Functional Air Electrode with Remarkable Stability for Rechargeable Zinc-Air Batteries. Nano-Micro Lett. 2020, 12, 130. [Google Scholar] [CrossRef]
  44. Christy, M.; Rajan, H.; Lee, H.; Rabani, I.; Koo, S.M.; Yi, S.C. Surface Engineering of Perovskites for Rechargeable Zinc-Air Battery Application. ACS Appl. Energy Mater. 2021, 4, 1876–1886. [Google Scholar] [CrossRef]
  45. Yang, L.; Yu, G.; Ai, X.; Yan, W.; Duan, H.; Chen, W.; Li, X.; Wang, T.; Zhang, C.; Huang, X.; et al. Efficient Oxygen Evolution Electrocatalysis in Acid by a Perovskite with Face-Sharing IrO6 Octahedral Dimers. Nat. Commun. 2018, 9, 5236. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  46. Edgington, J.; Schweitzer, N.; Alayoglu, S.; Seitz, L.C. Constant Change: Exploring Dynamic Oxygen Evolution Reaction Catalysis and Material Transformations in Strontium Zinc Iridate Perovskite in Acid. J. Am. Chem. Soc. 2021, 143, 9961–9971. [Google Scholar] [CrossRef] [PubMed]
  47. Chen, Y.; Li, H.; Wang, J.; Du, Y.; Xi, S.; Sun, Y.; Sherburne, M.; Ager, J.W.; Fisher, A.C.; Xu, Z.J. Exceptionally Active Iridium Evolved from a Pseudo-Cubic Perovskite for Oxygen Evolution in Acid. Nat. Commun. 2019, 10, 572. [Google Scholar] [CrossRef] [Green Version]
  48. Zhang, X.; Xu, X.; Yao, S.; Hao, C.; Pan, C.; Xiang, X.; Tian, Z.Q.; Shen, P.K.; Shao, Z.; Jiang, S.P. Boosting Electrocatalytic Activity of Single Atom Catalysts Supported on Nitrogen-Doped Carbon through N Coordination Environment Engineering. Small 2022, 18, 2105329. [Google Scholar] [CrossRef]
  49. Lee, J.S.; Kim, S.T.; Cao, R.; Choi, N.S.; Liu, M.; Lee, K.T.; Cho, J. Metal-Air Batteries with High Energy Density: Li-Air versus Zn-Air. Adv. Energy Mater. 2011, 1, 34–50. [Google Scholar] [CrossRef]
  50. Ma, H.; Wang, B.; Fan, Y.; Hong, W. Development and Characterization of an Electrically Rechargeable Zinc-Air Battery Stack. Energies 2014, 7, 6549–6557. [Google Scholar] [CrossRef]
  51. Li, P.C.; Chien, Y.J.; Hu, C.C. Novel Configuration of Bifunctional Air Electrodes for Rechargeable Zinc-Air Batteries. J. Power Sources 2016, 313, 37–45. [Google Scholar] [CrossRef]
  52. Hong, W.; Li, H.; Wang, B. A Horizontal Three-Electrode Structure for Zinc-Air Batteries with Long-Term Cycle Life and High Performance. Int. J. Electrochem. Sci. 2016, 11, 3843–3851. [Google Scholar] [CrossRef]
  53. Park, M.G.; Lee, D.U.; Seo, M.H.; Cano, Z.P.; Chen, Z. 3D Ordered Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries. Small 2016, 12, 2707–2714. [Google Scholar] [CrossRef] [PubMed]
  54. Bidault, F.; Brett, D.J.L.; Middleton, P.H.; Brandon, N.P. Review of Gas Diffusion Cathodes for Alkaline Fuel Cells. J. Power Sources 2009, 187, 39–48. [Google Scholar] [CrossRef]
  55. Gouérec, P.; Poletto, L.; Denizot, J.; Sanchez-Cortezon, E.; Miners, J.H. The Evolution of the Performance of Alkaline Fuel Cells with Circulating Electrolyte. J. Power Sources 2004, 129, 193–204. [Google Scholar] [CrossRef]
  56. Wang, X.; Lu, X.; Liu, B.; Chen, D.; Tong, Y.; Shen, G. Flexible Energy-Storage Devices: Design Consideration and Recent Progress. Adv. Mater. 2014, 26, 4763–4782. [Google Scholar] [CrossRef]
  57. Liu, Q.; Wang, Y.; Dai, L.; Yao, J. Scalable Fabrication of Nanoporous Carbon Fiber Films as Bifunctional Catalytic Electrodes for Flexible Zn-Air Batteries. Adv. Mater. 2016, 28, 3000–3006. [Google Scholar] [CrossRef] [PubMed]
  58. Fu, J.; Zhang, J.; Song, X.; Zarrin, H.; Tian, X.; Qiao, J.; Rasen, L.; Li, K.; Chen, Z. A Flexible Solid-State Electrolyte for Wide-Scale Integration of Rechargeable Zinc-Air Batteries. Energy Environ. Sci. 2016, 9, 663–670. [Google Scholar] [CrossRef]
  59. Zhang, Y.; Deng, Y.P.; Wang, J.; Jiang, Y.; Cui, G.; Shui, L.; Yu, A.; Wang, X.; Chen, Z. Recent Progress on Flexible Zn-Air Batteries. Energy Storage Mater. 2021, 35, 538–549. [Google Scholar] [CrossRef]
  60. Fang, W.; Zhao, J.; Zhang, W.; Chen, P.; Bai, Z.; Wu, M. Recent Progress and Future Perspectives of Flexible Zn-Air Batteries. J. Alloys Compd. 2021, 869, 158918. [Google Scholar] [CrossRef]
  61. Lai, S.B.; Jamesh, M.I.; Wu, X.C.; Dong, Y.L.; Wang, J.H.; Gao, M.; Liu, J.F.; Sun, X.M. A Promising Energy Storage System: Rechargeable Ni-Zn Battery. Rare Met. 2017, 36, 381–396. [Google Scholar] [CrossRef]
  62. Mainar, A.R.; Colmenares, L.C.; Blázquez, J.A.; Urdampilleta, I. A Brief Overview of Secondary Zinc Anode Development: The Key of Improving Zinc-Based Energy Storage Systems. Int. J. Energy Res. 2018, 42, 903–918. [Google Scholar] [CrossRef]
  63. Yan, Z.; Wang, E.; Jiang, L.; Sun, G. Superior Cycling Stability and High Rate Capability of Three-Dimensional Zn/Cu Foam Electrodes for Zinc-Based Alkaline Batteries. RSC Adv. 2015, 5, 83781–83787. [Google Scholar] [CrossRef]
  64. Li, P.; Jin, Z.; Xiao, D. Three-Dimensional Nanotube-Array Anode Enables a Flexible Ni/Zn Fibrous Battery to Ultrafast Charge and Discharge in Seconds. Energy Storage Mater. 2018, 12, 232–240. [Google Scholar] [CrossRef]
  65. Li, M.; Meng, J.; Li, Q.; Huang, M.; Liu, X.; Owusu, K.A.; Liu, Z.; Mai, L. Finely Crafted 3D Electrodes for Dendrite-Free and High-Performance Flexible Fiber-Shaped Zn-Co Batteries. Adv. Funct. Mater. 2018, 28, 1802016. [Google Scholar] [CrossRef]
  66. Lee, D.U.; Fu, J.; Park, M.G.; Liu, H.; Ghorbani Kashkooli, A.; Chen, Z. Self-Assembled NiO/Ni(OH)2 Nanoflakes as Active Material for High-Power and High-Energy Hybrid Rechargeable Battery. Nano Lett. 2016, 16, 1794–1802. [Google Scholar] [CrossRef]
  67. Huang, Z.; Li, X.; Yang, Q.; Ma, L.; Mo, F.; Liang, G.; Wang, D.; Liu, Z.; Li, H.; Zhi, C. Ni3S2/Ni Nanosheet Arrays for High-Performance Flexible Zinc Hybrid Batteries with Evident Two-Stage Charge and Discharge Processes. J. Mater. Chem. A 2019, 7, 18915–18924. [Google Scholar] [CrossRef]
  68. Zhong, X.; Ye, S.; Tang, J.; Zhu, Y.; Wu, D.; Gu, M.; Pan, H.; Xu, B. Engineering Pt and Fe Dual-Metal Single Atoms Anchored on Nitrogen-Doped Carbon with High Activity and Durability towards Oxygen Reduction Reaction for Zinc-Air Battery. Appl. Catal. B Environ. 2021, 286, 119891. [Google Scholar] [CrossRef]
  69. Liua, P.; Hub, Y.; Wanga, L.; Tongtong, X.; Xid, X.; Gaoa, P.; Daqiang, S.; Wangb, J. Cu and Co Nanoparticle Co-Decorated N-Doped Graphene Nanosheets: A High Efficiency Bifunctional Electrocatalyst for Rechargeable Zn-Air Batteries. J. Mater. Chem. A 2019, 20, 26116–26122. [Google Scholar] [CrossRef]
  70. Zhang, G.; Liu, X.; Wang, L.; Xing, G.; Tian, C.; Fu, H. Copper Collector Generated Cu+/Cu2+ Redox Pair for Enhanced Efficiency and Lifetime of Zn-Ni/Air Hybrid Battery. ACS Nano 2022, 16, 17139–17148. [Google Scholar] [CrossRef]
  71. Liu, B.; Yu, S.H.; Li, L.; Zhang, Q.; Zhang, F.; Jiang, K. Morphology Control of Stolzite Microcrystals with High Hierarchy in Solution. Angew. Chem. 2004, 116, 4849–4854. [Google Scholar] [CrossRef]
  72. Xie, X.; Shen, W. Morphology Control of Cobalt Oxide Nanocrystals for Promoting Their Catalytic Performance. Nanoscale 2009, 1, 50–60. [Google Scholar] [CrossRef]
  73. Roberts, A.D.; Li, X.; Zhang, H. Porous Carbon Spheres and Monoliths: Morphology Control, Pore Size Tuning and Their Applications as Li-Ion Battery Anode Materials. Chem. Soc. Rev. 2014, 43, 4341–4356. [Google Scholar] [CrossRef]
  74. Orilall, M.C.; Wiesner, U. Block Copolymer Based Composition and Morphology Control in Nanostructured Hybrid Materials for Energy Conversion and Storage: Solar Cells, Batteries, and Fuel Cells. Chem. Soc. Rev. 2011, 40, 520–535. [Google Scholar] [CrossRef]
  75. Sau, T.K.; Rogach, A.L. Nonspherical Noble Metal Nanoparticles: Colloid-Chemical Synthesis and Morphology Control. Adv. Mater. 2010, 22, 1781–1804. [Google Scholar] [CrossRef]
  76. Ma, K.; Chen, W.; Jiao, T.; Jin, X.; Sang, Y.; Yang, D.; Zhou, J.; Liu, M.; Duan, P. Boosting the Circularly Polarized Luminescence of Small Organic Molecules: Via Multi-Dimensional Morphology Control. Chem. Sci. 2019, 10, 6821–6827. [Google Scholar] [CrossRef] [Green Version]
  77. Bu, Y.; Jang, H.; Gwon, O.; Kim, S.H.; Joo, S.H.; Nam, G.; Kim, S.; Qin, Y.; Zhong, Q.; Kwak, S.K.; et al. Synergistic Interaction of Perovskite Oxides and N-Doped Graphene in Versatile Electrocatalyst. J. Mater. Chem. A 2019, 7, 2048–2054. [Google Scholar] [CrossRef]
  78. Ji, Q.; Bi, L.; Zhang, J.; Cao, H.; Zhao, X.S. The Role of Oxygen Vacancies of ABO3 perovskite Oxides in the Oxygen Reduction Reaction. Energy Environ. Sci. 2020, 13, 1408–1428. [Google Scholar] [CrossRef]
  79. Safakas, A.; Bampos, G.; Bebelis, S. Oxygen Reduction Reaction on La0.8Sr0.2CoxFe1−xO3−δ Perovskite/Carbon Black Electrocatalysts in Alkaline Medium. Appl. Catal. B Environ. 2019, 244, 225–232. [Google Scholar] [CrossRef]
  80. Dong, P.; Hou, G.; Xi, X.; Shao, R.; Dong, F. WO3-Based Photocatalysts: Morphology Control, Activity Enhancement and Multifunctional Applications. Environ. Sci. Nano 2017, 4, 539–557. [Google Scholar] [CrossRef]
  81. Sun, Y.; Lin, H.; Wang, C.; Wu, Q.; Wang, X.; Yang, M. Morphology-Controlled Synthesis of TiO2/MoS2 Nanocomposites with Enhanced Visible-Light Photocatalytic Activity. Inorg. Chem. Front. 2018, 5, 145–152. [Google Scholar] [CrossRef]
  82. Wang, Q.; Xue, Y.; Sun, S.; Li, S.; Miao, H.; Liu, Z. La0.8Sr0.2Co1−xMnxO3 Perovskites as Efficient Bi-Functional Cathode Catalysts for Rechargeable Zinc-Air Batteries. Electrochim. Acta 2017, 254, 14–24. [Google Scholar] [CrossRef]
  83. Navas, D.; Fuentes, S.; Castro-Alvarez, A.; Chavez-Angel, E. Review on Sol-Gel Synthesis of Perovskite and Oxide Nanomaterials. Gels 2021, 7, 275. [Google Scholar] [CrossRef]
  84. Zhong, Z.; Chen, K.; Ji, Y.; Yan, Q. Methane Combustion over B-Site Partially Substituted Perovskite-Type LaFeO3 Prepared by Sol-Gel Method. Appl. Catal. A Gen. 1997, 156, 29–41. [Google Scholar] [CrossRef]
  85. Fabbri, E.; Nachtegaal, M.; Binninger, T.; Cheng, X.; Kim, B.J.; Durst, J.; Bozza, F.; Graule, T.; Schäublin, R.; Wiles, L.; et al. Dynamic Surface Self-Reconstruction Is the Key of Highly Active Perovskite Nano-Electrocatalysts for Water Splitting. Nat. Mater. 2017, 16, 925–931. [Google Scholar] [CrossRef]
  86. Spöri, C.; Kwan, J.T.H.; Bonakdarpour, A.; Wilkinson, D.P.; Strasser, P. The Stability Challenges of Oxygen Evolving Electrocatalysts: Towards a Common Fundamental Understanding and Mitigation of Catalyst Degradation. Angew. Chem. Int. Ed. 2017, 56, 5994–6021. [Google Scholar] [CrossRef]
  87. Keeble, D.J.; Wicklein, S.; Dittmann, R.; Ravelli, L.; MacKie, R.A.; Egger, W. Identification of A- and B-Site Cation Vacancy Defects in Perovskite Oxide Thin Films. Phys. Rev. Lett. 2010, 105, 3–6. [Google Scholar] [CrossRef] [Green Version]
  88. Zhu, Y.; Zhang, L.; Zhao, B.; Chen, H.; Liu, X.; Zhao, R.; Wang, X.; Liu, J.; Chen, Y.; Liu, M. Improving the Activity for Oxygen Evolution Reaction by Tailoring Oxygen Defects in Double Perovskite Oxides. Adv. Funct. Mater. 2019, 29, 1901783. [Google Scholar] [CrossRef]
  89. Zhu, Y.; Zhong, X.; Jin, S.; Chen, H.; He, Z.; Liu, Q.; Chen, Y. Oxygen Defect Engineering in Double Perovskite Oxides for Effective Water Oxidation. J. Mater. Chem. A 2020, 8, 10957–10965. [Google Scholar] [CrossRef]
  90. Gupta, S.; Kellogg, W.; Xu, H.; Liu, X.; Cho, J.; Wu, G. Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media. Chem. Asian J. 2016, 11, 10–21. [Google Scholar] [CrossRef] [PubMed]
  91. Majee, R.; Das, T.; Chakraborty, S.; Bhattacharyya, S. Shaping a Doped Perovskite Oxide with Measured Grain Boundary Defects to Catalyze Bifunctional Oxygen Activation for a Rechargeable Zn-Air Battery. ACS Appl. Mater. Interfaces 2020, 12, 40355–40363. [Google Scholar] [CrossRef]
  92. Jung, J.I.; Park, S.; Kim, M.G.; Cho, J. Tunable Internal and Surface Structures of the Bifunctional Oxygen Perovskite Catalysts. Adv. Energy Mater. 2015, 5, 1501560. [Google Scholar] [CrossRef]
  93. Suntivich, J.; Gasteiger, H.A.; Yabuuchi, N.; Nakanishi, H.; Goodenough, J.B.; Shao-Horn, Y. Design Principles for Oxygen-Reduction Activity on Perovskite Oxide Catalysts for Fuel Cells and Metal-Air Batteries. Nat. Chem. 2011, 3, 546–550. [Google Scholar] [CrossRef] [PubMed]
  94. Matsumoto, Y.; Yoneyama, H.; Tamura, H. Catalytic Activity for Electrochemical Reduction of Oxygen of Lanthanum Nickel Oxide and Related Oxides. J. Electroanal. Chem. Interfac. Electrochem. 1977, 79, 319–326. [Google Scholar] [CrossRef]
  95. Shao, Z.; Yang, W.; Cong, Y.; Dong, H.; Tong, J.; Xiong, G. Investigation of the Permeation Behavior and Stability of a Ba0.5Sr0.5Co0.8Fe0.2O(3−δ) Oxygen Membrane. J. Membr. Sci. 2000, 172, 177–188. [Google Scholar] [CrossRef]
  96. Shao, Z.; Halle, S.M. A High-Performance Cathode for the next Generation of Solid-Oxide Fuel Cells. Nature 2004, 431, 170–173. [Google Scholar] [CrossRef] [PubMed]
  97. Shao, Z.; Mederos, J.; Chueh, W.C.; Haile, S.M. High Power-Density Single-Chamber Fuel Cells Operated on Methane. J. Power Sources 2006, 162, 589–596. [Google Scholar] [CrossRef]
  98. Li, Q.; Cao, R.; Cho, J.; Wu, G. Nanocarbon Electrocatalysts for Oxygen Reduction in Alkaline Media for Advanced Energy Conversion and Storage. Adv. Energy Mater. 2014, 4, 1301415. [Google Scholar] [CrossRef]
  99. Wu, X.; Miao, H.; Hu, R.; Chen, B.; Yin, M.; Zhang, H.; Xia, L.; Zhang, C.; Yuan, J. A-Site Deficient Perovskite Nanofibers Boost Oxygen Evolution Reaction for Zinc-Air Batteries. Appl. Surf. Sci. 2021, 536, 147806. [Google Scholar] [CrossRef]
  100. Jiang, L.; Yuan, X.; Pan, Y.; Liang, J.; Zeng, G.; Wu, Z.; Wang, H. Doping of Graphitic Carbon Nitride for Photocatalysis: A Reveiw. Appl. Catal. B Environ. 2017, 217, 388–406. [Google Scholar] [CrossRef]
  101. Ghosh, K.; Ogale, S.B.; Ramesh, R.; Greene, R.L.; Venkatesan, T.; Gapchup, K.M.; Bathe, R.; Patil, S.I. Transition-Element Doping Effects in La0.7Ca0.3MnO3. Phys. Rev. B Condens. Matter Mater. Phys. 1999, 59, 533–537. [Google Scholar] [CrossRef]
  102. Deng, S.; Luo, M.; Ai, C.; Zhang, Y.; Liu, B.; Huang, L.; Jiang, Z.; Zhang, Q.; Gu, L.; Lin, S.; et al. Synergistic Doping and Intercalation: Realizing Deep Phase Modulation on MoS2 Arrays for High-Efficiency Hydrogen Evolution Reaction. Angew. Chemie Int. Ed. 2019, 58, 16289–16296. [Google Scholar] [CrossRef] [PubMed]
  103. Zhang, Y.; Ji, H.; Ma, W.; Chen, C.; Song, W.; Zhao, J. Doping-Promoted Solar Water Oxidation on Hematite Photoanodes. Molecules 2016, 21, 868. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  104. Patnaik, S.; Sahoo, D.P.; Parida, K. Recent Advances in Anion Doped G-C3N4 Photocatalysts: A Review. Carbon 2021, 172, 682–711. [Google Scholar] [CrossRef]
  105. Zeng, K.; Li, C.; Lu, J.; Sun, J.; Pan, X.; Jin, C.; Wei, M.; Yang, R. A-Site Doped Perovskite Oxide Strongly Interface Coupling with Carbon Nanotubes as a Promising Bifunctional Electrocatalyst for Solid-State Zn-Air Batteries. Energy Fuels 2021, 35, 12700–12705. [Google Scholar] [CrossRef]
  106. Ran, J.; Wang, T.; Zhang, J.; Liu, Y.; Xu, C.; Xi, S.; Gao, D. Modulation of Electronics of Oxide Perovskites by Sulfur Doping for Electrocatalysis in Rechargeable Zn-Air Batteries. Chem. Mater. 2020, 32, 3439–3446. [Google Scholar] [CrossRef]
  107. Liu, Y.; Wang, W.; Xu, X.; Marcel Veder, J.P.; Shao, Z. Recent Advances in Anion-Doped Metal Oxides for Catalytic Applications. J. Mater. Chem. A 2019, 7, 7280–7300. [Google Scholar] [CrossRef]
  108. Zhang, C.; Wang, Y.; Lin, X.; Wu, T.; Han, Q.; Zhang, Y.; Han, L. Effects of A Site Doping on the Crystallization of Perovskite Films. J. Mater. Chem. A 2021, 9, 1372–1394. [Google Scholar] [CrossRef]
  109. Qin, M.; Xue, H.; Zhang, H.; Hu, H.; Liu, K.; Li, Y.; Qin, Z.; Ma, J.; Zhu, H.; Yan, K.; et al. Precise Control of Perovskite Crystallization Kinetics via Sequential A-Site Doping. Adv. Mater. 2020, 32, 2004630. [Google Scholar] [CrossRef]
  110. Li, X.; Zhao, H.; Liang, J.; Luo, Y.; Chen, G.; Shi, X.; Lu, S.; Gao, S.; Hu, J.; Liu, Q.; et al. A-Site Perovskite Oxides: An Emerging Functional Material for Electrocatalysis and Photocatalysis. J. Mater. Chem. A 2021, 9, 6650–6670. [Google Scholar] [CrossRef]
  111. Jung, J.; Risch, M.; Park, S.; Kim, M.G.; Nam, G.; Jeong, H.; Shao-Horn, Y.; Cho, J. Optimizing Nanoparticle Perovskite for Bifunctional Oxygen Electrocatalysis. Energy Environ. Sci. 2016, 9, 176–183. [Google Scholar] [CrossRef] [Green Version]
  112. Gao, X.Y.; Sun, X.W.; Guo, J.H.; Teng, Y.N.; Liu, L.; Xu, G.R.; Xu, T.; Liu, H.; Bai, J.; Li, C.P. B-Site W Ion-Doped La0.5Sr0.5Co1−xWxO3−δ perovskite Nanofibers with Defects as Bifunctional Oxygen Catalysts for Rechargeable Zinc-Air Batteries. Sustain. Energy Fuels 2021, 5, 3818–3824. [Google Scholar] [CrossRef]
  113. Kim, N.I.; Cho, S.H.; Park, S.H.; Lee, Y.J.; Afzal, R.A.; Yoo, J.; Seo, Y.S.; Lee, Y.J.; Park, J.Y. B-Site Doping Effects of NdBa0.75Ca0.25Co2O5+δ Double Perovskite Catalysts for Oxygen Evolution and Reduction Reactions. J. Mater. Chem. A 2018, 6, 17807–17818. [Google Scholar] [CrossRef]
  114. Karuppiah, C.; Thirumalraj, B.; Alagar, S.; Piraman, S.; Li, Y.J.J.; Yang, C.C. Solid-State Ball-Milling of Co3O4 Nano/Microspheres and Carbon Black Endorsed LaMnO3 Perovskite Catalyst for Bifunctional Oxygen Electrocatalysis. Catalysts 2021, 11, 76. [Google Scholar] [CrossRef]
  115. Lee, D.U.; Park, H.W.; Park, M.G.; Ismayilov, V.; Chen, Z. Synergistic Bifunctional Catalyst Design Based on Perovskite Oxide Nanoparticles and Intertwined Carbon Nanotubes for Rechargeable Zinc-Air Battery Applications. ACS Appl. Mater. Interfaces 2015, 7, 902–910. [Google Scholar] [CrossRef]
  116. Lee, H.; Gwon, O.; Lim, C.; Kim, J.; Galindev, O.; Kim, G. Advanced Electrochemical Properties of PrBa0.5Sr0.5Co1.9Ni0.1O5+δ as a Bifunctional Catalyst for Rechargeable Zinc-Air Batteries. ChemElectroChem 2019, 6, 3154–3159. [Google Scholar] [CrossRef]
  117. Bu, Y.; Gwon, O.; Nam, G.; Jang, H.; Kim, S.; Zhong, Q.; Cho, J.; Kim, G. A Highly Efficient and Robust Cation Ordered Perovskite Oxide as a Bifunctional Catalyst for Rechargeable Zinc-Air Batteries. ACS Nano 2017, 11, 11594–11601. [Google Scholar] [CrossRef]
  118. Majee, R.; Islam, Q.A.; Bhattacharyya, S. Surface Charge Modulation of Perovskite Oxides at the Crystalline Junction with Layered Double Hydroxide for a Durable Rechargeable Zinc-Air Battery. ACS Appl. Mater. Interfaces 2019, 11, 35853–35862. [Google Scholar] [CrossRef]
  119. Zhang, Y.; Guo, Y.; Liu, T.; Feng, F.; Wang, C.; Hu, H.; Wu, M.; Ni, M.; Shao, Z. The Synergistic Effect Accelerates the Oxygen Reduction/Evolution Reaction in a Zn-Air Battery. Front. Chem. 2019, 7, 524. [Google Scholar] [CrossRef] [Green Version]
  120. Yan, S.; Xue, Y.; Li, S.; Shao, G.; Liu, Z. Enhanced Bifunctional Catalytic Activity of Manganese Oxide/Perovskite Hierarchical Core-Shell Materials by Adjusting the Interface for Metal-Air Batteries. ACS Appl. Mater. Interfaces 2019, 11, 25870–25881. [Google Scholar] [CrossRef]
  121. Peng, S.; Han, X.; Li, L.; Chou, S.; Ji, D.; Huang, H.; Du, Y.; Liu, J.; Ramakrishna, S. Electronic and Defective Engineering of Electrospun CaMnO3 Nanotubes for Enhanced Oxygen Electrocatalysis in Rechargeable Zinc-Air Batteries. Adv. Energy Mater. 2018, 8, 1800612. [Google Scholar] [CrossRef]
  122. Bian, J.; Li, Z.; Li, N.; Sun, C. Oxygen Deficient LaMn0.75Co0.25O3−δ Nanofibers as an Efficient Electrocatalyst for Oxygen Evolution Reaction and Zinc-Air Batteries. Inorg. Chem. 2019, 58, 8208–8214. [Google Scholar] [CrossRef]
  123. Vignesh, A.; Prabu, M.; Shanmugam, S. Porous LaCo1−xNixO3−δ Nanostructures as an Efficient Electrocatalyst for Water Oxidation and for a Zinc-Air Battery. ACS Appl. Mater. Interfaces 2016, 8, 6019–6031. [Google Scholar] [CrossRef]
  124. Yuan, R.H.; He, Y.; He, W.; Ni, M.; Leung, M.K.H. Bifunctional Electrocatalytic Activity of La0.8Sr0.2MnO3−δ Based Perovskite with the A-Site Deficiency for Oxygen Reduction and Evolution Reactions in Alkaline Media. Appl. Energy 2019, 251, 113406. [Google Scholar] [CrossRef]
  125. Bian, J.; Su, R.; Yao, Y.; Wang, J.; Zhou, J.; Li, F.; Wang, Z.L.; Sun, C. Mg Doped Perovskite LaNiO3 Nanofibers as an Efficient Bifunctional Catalyst for Rechargeable Zinc-Air Batteries. ACS Appl. Energy Mater. 2019, 2, 923–931. [Google Scholar] [CrossRef]
  126. Zhang, Y.Q.; Tao, H.B.; Chen, Z.; Li, M.; Sun, Y.F.; Hua, B.; Luo, J.L. In Situ Grown Cobalt Phosphide (CoP) on Perovskite Nanofibers as an Optimized Trifunctional Electrocatalyst for Zn-Air Batteries and Overall Water Splitting. J. Mater. Chem. A 2019, 7, 26607–26617. [Google Scholar] [CrossRef]
  127. Gui, L.; Wang, Z.; Zhang, K.; He, B.; Liu, Y.; Zhou, W.; Xu, J.; Wang, Q.; Zhao, L. Oxygen Vacancies-Rich Ce0.9Gd0.1O2−δ Decorated Pr0.5Ba0.5CoO3−δ Bifunctional Catalyst for Efficient and Long-Lasting Rechargeable Zn-Air Batteries. Appl. Catal. B Environ. 2020, 266, 118656. [Google Scholar] [CrossRef]
  128. Yan, Z.; Sun, H.; Chen, X.; Fu, X.; Chen, C.; Cheng, F.; Chen, J. Rapid Low-Temperature Synthesis of Perovskite/Carbon Nanocomposites as Superior Electrocatalysts for Oxygen Reduction in Zn-Air Batteries. Nano Res. 2018, 11, 3282–3293. [Google Scholar] [CrossRef]
  129. Mondal, S.; Majee, R.; Arif Islam, Q.; Bhattacharyya, S. 2D Heterojunction Between Double Perovskite Oxide Nanosheet and Layered Double Hydroxide to Promote Rechargeable Zinc-Air Battery Performance. ChemElectroChem 2020, 7, 5005–5012. [Google Scholar] [CrossRef]
  130. Nie, R.; Deng, Y.; Yang, H.; Tan, Y.; Yuan, H.; Sagar, R.U.R.; Liang, T. Efficient Oxygen Evolution Reaction in SrCo0.8Fe0.2O3−δ Perovskite and Surface Reconstruction for Practical Zinc-Air Batteries. Appl. Surf. Sci. 2021, 552, 149509. [Google Scholar] [CrossRef]
  131. Li, P.; Wei, B.; Lü, Z.; Wu, Y.; Zhang, Y.; Huang, X. La1.7Sr0.3Co0.5Ni0.5O4+δ Layered Perovskite as an Efficient Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries. Appl. Surf. Sci. 2019, 464, 494–501. [Google Scholar] [CrossRef]
  132. Zhuang, S.; Wang, Z.; He, J.; Jia, D.; Wang, Q.; Lu, M.; Tu, F. Perovskite La0.5Ca0.5CoO3−δ Nanocrystals on Graphene as a Synergistic Catalyst for Rechargeable Zinc-Air Batteries. Sustain. Mater. Technol. 2021, 29, e00282. [Google Scholar] [CrossRef]
  133. Bhardwaj, U.; Sharma, A.; Gupta, V.; Batoo, K.M.; Hussain, S.; Kushwaha, H.S. High Energy Storage Capabilities of CaCu3Ti4O12 for Paper-Based Zinc-Air Battery. Sci. Rep. 2022, 12, 3999. [Google Scholar] [CrossRef] [PubMed]
  134. Bhardwaj, U.; Sharma, A.; Mathur, A.; Halder, A.; Kushwaha, H.S. Synthesis of a Novel Sr2TiMnO6 Double Perovskite Electrocatalyst for Rechargeable Zinc-Air Batteries. Energy Storage 2022, 4, e293. [Google Scholar] [CrossRef]
  135. Li, K.; Dong, Z.; Lü, Z. Study of the Bifunctional Catalytic Activity on Sr and Mn Co-Doped PrFeO3−δ Zinc-Air Batteries Cathode. Electrochim. Acta 2022, 430, 141123. [Google Scholar] [CrossRef]
  136. Liu, H.; Ren, X.; Bai, H.; Qiao, H.; Lu, J.; Wang, X.; Huang, H.; Hu, J. 2LaCo0.7Fe0.3O3/N-Doped Carbon Bifunctional Electrocatalyst Derived from g-C3N4 Nanosheets for Zinc-Air Battery. Electrochim. Acta 2022, 414, 140211. [Google Scholar] [CrossRef]
  137. Yuan, R.H.; Chen, B.; Zhang, Y.; Tan, F.; Liu, T. Boosting the Bifunctional Electrocatalytic Activity of Cobalt Free Perovskite Oxide (La0.8Sr0.2)0.95MnO3 via Iron Doping for High-Efficiency Zn-Air Batteries. Sep. Purif. Technol. 2022, 300, 121858. [Google Scholar] [CrossRef]
  138. Struben, J.; Sterman, J. Transition Challenges for Alternative Fuel Vehicle and Transportation Systems. SSRN Electron. J. 2008, 35, 1070–1097. [Google Scholar] [CrossRef]
  139. Ou, X.; Zhang, X.; Chang, S. Scenario Analysis on Alternative Fuel/Vehicle for China’s Future Road Transport: Life-Cycle Energy Demand and GHG Emissions. Energy Policy 2010, 38, 3943–3956. [Google Scholar] [CrossRef]
  140. Pan, J.; Xu, Y.Y.; Yang, H.; Dong, Z.; Liu, H.; Xia, B.Y. Advanced Architectures and Relatives of Air Electrodes in Zn-Air Batteries. Adv. Sci. 2018, 5, 1700691. [Google Scholar] [CrossRef]
  141. Prakoso, B.; Mahbub, M.A.A.; Yilmaz, M.; Khoiruddin; Wenten, I.G.; Handoko, A.D.; Sumboja, A. Recent Progress in Extending the Cycle-Life of Secondary Zn-Air Batteries. ChemNanoMat 2021, 7, 354–367. [Google Scholar] [CrossRef]
  142. John, F.C.; Dennis, F.; Larry, K.; Arturo, M.; Keith, P.; Ronald, K. Demonstration of a Zinc/Air Fuel Battery to Enhance the Range and Mission of Fleet Electric Vehicles: Preliminary Results in the Refueling of a Multicell Module; Lawrence Livermore National Laboratory: Livermore, CA, USA, 1994. [Google Scholar]
  143. Jonathan, R.G.; Binyamin, K. Tests of a Full-Sized Mechanically Rechargeable Zinc-Air Battery in an Electric Vehicle. IEEE Aerosp. Electron. Syst. Mag. 1993, 8, 34–38. [Google Scholar] [CrossRef]
  144. de Sá, M.H.; Pinto, A.M.F.R.; Oliveira, V.B. Passive Direct Methanol Fuel Cells as a Sustainable Alternative to Batteries in Hearing Aid Devices—An Overview. Int. J. Hydrogen Energy 2022, 47, 16552–16567. [Google Scholar] [CrossRef]
  145. Sparkes, C. A Study of Mercuric Oxide and Zinc-Air Battery Life in Hearing Aids. J. Laryngol. Otol. 1997, 111, 814–819. [Google Scholar] [CrossRef]
  146. Jo, Y.N.; Prasanna, K.; Kang, S.H.; Ilango, P.R.; Kim, H.S.; Eom, S.W.; Lee, C.W. The Effects of Mechanical Alloying on the Self-Discharge and Corrosion Behavior in Zn-Air Batteries. J. Ind. Eng. Chem. 2017, 53, 247–252. [Google Scholar] [CrossRef]
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Figure 1. Modulation strategies of perovskite oxide for applications in zinc-air batteries.
Figure 1. Modulation strategies of perovskite oxide for applications in zinc-air batteries.
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Figure 3. (a) TEM image of P-3G; (b) The charge transfer from 3DNG to PBSCF (left) and the schematic band diagrams of PBSCF and PBSCF with 3DNG (right); (c,d) ORR and OER LSV curves; (e) Power density curves; (f) Discharge and charge cycling curves of rechargeable ZABs based on P-3G and Pt/C+IrO2 at a current density of 10 mA cm−2 [77]. Copyright 2018, the Royal Society of Chemistry.
Figure 3. (a) TEM image of P-3G; (b) The charge transfer from 3DNG to PBSCF (left) and the schematic band diagrams of PBSCF and PBSCF with 3DNG (right); (c,d) ORR and OER LSV curves; (e) Power density curves; (f) Discharge and charge cycling curves of rechargeable ZABs based on P-3G and Pt/C+IrO2 at a current density of 10 mA cm−2 [77]. Copyright 2018, the Royal Society of Chemistry.
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Figure 6. (a) XPS spectrum of Co 2p; (b,c) Co-K edge XANES and EXAFS spectra of sulfur-doped LaCoO3; (d) the evolution of the Intermediate spin state and the transition of electrons from t2g to eg orbital (e) power density; (f,g) the stability of aqueous ZABs and flexible ZABs [106]. Copyright 2020, American Chemical Society.
Figure 6. (a) XPS spectrum of Co 2p; (b,c) Co-K edge XANES and EXAFS spectra of sulfur-doped LaCoO3; (d) the evolution of the Intermediate spin state and the transition of electrons from t2g to eg orbital (e) power density; (f,g) the stability of aqueous ZABs and flexible ZABs [106]. Copyright 2020, American Chemical Society.
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Figure 7. (a) BFTEM image of La0.7-50 nm; (b) HAADF STEM image showing the atomic arrangements of cubic perovskite structure in {100} direction and schematic of a perovskite unit cell; (c) X-ray diffraction patterns for La0.7-50 nm, La0.7-100 nm and La0.1-1 µm; (d) Normalized Co and Fe K-edge XANES spectra; (e) RDFs of Fourier-transformed k3-weighted EXAFS spectra [111]. Copyright 2015, the Royal Society of Chemistry.
Figure 7. (a) BFTEM image of La0.7-50 nm; (b) HAADF STEM image showing the atomic arrangements of cubic perovskite structure in {100} direction and schematic of a perovskite unit cell; (c) X-ray diffraction patterns for La0.7-50 nm, La0.7-100 nm and La0.1-1 µm; (d) Normalized Co and Fe K-edge XANES spectra; (e) RDFs of Fourier-transformed k3-weighted EXAFS spectra [111]. Copyright 2015, the Royal Society of Chemistry.
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Zhu, Z.; Song, Q.; Xia, B.; Jiang, L.; Duan, J.; Chen, S. Perovskite Catalysts for Oxygen Evolution and Reduction Reactions in Zinc-Air Batteries. Catalysts 2022, 12, 1490. https://0-doi-org.brum.beds.ac.uk/10.3390/catal12121490

AMA Style

Zhu Z, Song Q, Xia B, Jiang L, Duan J, Chen S. Perovskite Catalysts for Oxygen Evolution and Reduction Reactions in Zinc-Air Batteries. Catalysts. 2022; 12(12):1490. https://0-doi-org.brum.beds.ac.uk/10.3390/catal12121490

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Zhu, Zheng, Qiangqiang Song, Baokai Xia, Lili Jiang, Jingjing Duan, and Sheng Chen. 2022. "Perovskite Catalysts for Oxygen Evolution and Reduction Reactions in Zinc-Air Batteries" Catalysts 12, no. 12: 1490. https://0-doi-org.brum.beds.ac.uk/10.3390/catal12121490

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