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A Nano-Architectured Metal-Oxide/Perovskite Hybrid Material as Electrocatalyst for the Oxygen Reduction Reaction in Aluminum–Air Batteries Yejian Xue, Shanshan Yan, Heran Huang, and Zhaoping Liu ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.8b01630 • Publication Date (Web): 28 Nov 2018 Downloaded from http://pubs.acs.org on November 30, 2018

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ACS Applied Nano Materials

A Nano-Architectured Metal-Oxide/Perovskite Hybrid Material as Electrocatalyst for the Oxygen Reduction Reaction in Aluminum–Air Batteries Yejian Xue, *,† Shanshan Yan, †,‡ Heran Huang,† and Zhaoping Liu *,†

†Ningbo

Institute of Materials Technology & Engineering, Chinese Academy of

Sciences, Zhejiang 315201, P. R. China ‡Hebei

Key Laboratory of applied chemistry, College of Environmental and Chemical

Engineering, Yanshan University, Qinhuangdao 066004, P. R. China

*Corresponding authors: Tel.: +86-574-8668-6430 Fax: +86-574-8668-5096, E-mail: [email protected], [email protected]

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ABSTRACT A nano-architectured La2O2CO3-La0.7Sr0.3MnO3 hybrid catalyst is prepared by a facile hydrothermal method. The La2O2CO3 nano-rods are well distributed on the regular hexagonal La0.7Sr0.3MnO3 nano-sheet. The La2O2CO3-La0.7Sr0.3MnO3 catalyst has better catalytic activity to oxygen reduction reaction than that of La2O2CO3 or La0.7Sr0.3MnO3. The reaction kinetics result shows that La2O2CO3-La0.7Sr0.3MnO3 sample follows a four-electron transferred process during oxygen reduction reaction. Furthermore, the stability of La2O2CO3-La0.7Sr0.3MnO3 is higher than that of Pt/C. By using La2O2CO3-La0.7Sr0.3MnO3 as the cathode catalysts for aluminum-air battery, the power densities can reach 223.8 mW cm−2. The high catalytic performance of the La2O2CO3-La0.7Sr0.3MnO3 can be attributed to the strong interaction between the La2O2CO3 material and La0.7Sr0.3MnO3 material. KEYWORDS: Aluminum-air battery, Composite material, Electrocatalyst, Oxygen reduction reaction, Transition metal oxide catalysts, Perovskite

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1.

INTRODUCTION Recently, the metal–air battery (MAB) has attracted the increasing

attention form researchers and technicians due to its low cost, high specific energy density and environment-friendly system.1-3 The design of MABs possess the feature of traditional battery using metal/alloy as the negative electrode material. They also have the special feature of a half-open system breathing the reactant of oxygen from the ambient air, which is akin to fuel cells.1 So far, serials of MABs have been developed including Zinc–air (Zn– air), Magnesium–air (Mg–air), Lithium–air (Li–air), Ferrum–air (Fe–air), Aluminum–air (Al–air), and so on.2, 4 Among them, Al-air battery is receiving the considerable attention due to its high theoretical specific energy density (4274 Wh kg−1, Al(OH)3 as the product and electrolyte inclusive).2, 4-6 In 2014, the Al–air battery system loaded with 100 kilogram aluminum metal has been developed by the Phinergy Company. They applied the battery system to an electric vehicle and extended the driving range of the car to over 1600 kilometre.4,7 However, there are still some outstanding problems such as high self-discharge rate of the Al/Al-alloy metal in alkaline electrolyte(generate hydrogen), high polarization resistance of the cathode electrode, low structural stability of the air-breathing cathode during the long-term operation, and the sluggish reaction kinetics of the oxygen electrocatalyst. The main issue arises from the catalysts due to the sluggish oxygen reduction reaction (ORR) process in practice.1,

4, 8-13

3


The ORR catalysts


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(ORRCs) are crucial components for the fuel cells and MABs.14-15 Up to now, there are many high catalytic activity catalysts been developed for the metal-air battery

including

the

noble

metals,

metal

oxides,

carbon

materials,

organometallic macrocycles and metal/nitrogen doped carbon nanomaterials.6, 16-18

Pt-based alloy catalysts have been extensively studied because of their high

oxygen reduction catalytic activity in basic electrolyte. However, the high cost and scarcity has limited the widespread use of these catalysts.19 In order to realize the extensive application of MABs, the most important task is exploiting the low-cost and efficient electrocatalysts for the ORR process. Therefore, many recent reports are concentrated on the study of metal oxide-based and carbon catalysts, such as the carbonaceous catalysts, Fe-N co-doped carbon materials, Cu − MOF derived Cu/Cu2O, Co/CoNx@C nanomaterials, Co3O4, MnO2, LaNiO3, LaCoO3, LaFeO3, and LaMnO3.1-2,7,14-18, 20-22 Some perovskite-based oxides have been promised as the considerable and potential ORRCs to substitute precious metal catalyst.23 The LaMnO3-based perovskite oxides have been widely investigated due to theirs high performance.23 Furthermore, the catalytic performance can be further promoted by doping the strontium element in A-site of the LaMnO3, which can be attributed to the manipulation of manganese-element valence state between Mn4+ and Mn3+.16,

22, 24-31

Recently, La2O3 or La2O3 modified materials have

been proposed as an efficient ORRCs in the alkaline solution.32-35 The La2O3 supported on carbon (carbonaceous micro-sphere) by a hydrothermal 4


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treatment,33 the La2O3-modified Co3O4/MnO2-Carbon-Nanotube composites35 and the La2O2CO3@La2O3/C hybrid prepared via chemical precipitation34 exhibited high catalytic activity for ORR. In this study, the La2O2CO3-La0.7Sr0.3MnO3 (LC-LSM) hybrid was synthetized as a high efficient ORRC by the hydrothermal method with a one-pot synthesis. Comparing with the La2O2CO3 (LC), La0.7Sr0.3MnO3 (LSM), the mixture of the above two materials (LC/LSM) in alkaline solution, the synthesized LC-LSM hybrid catalyst exhibits high catalytic activity toward ORR. Moreover, its long-term durability is also outperforming that of 20%Pt/C sample. The Pmax value (maximum power density) of the sample with LC-LSM is 223.8 mW cm−2; it is 1.4 times of that of LC sample. 2.

EXPERIMENTAL SECTION

2.1 Synthesis of LC-LSM hybrid material LC-LSM composite material was prepared by hydrothermal method. Firstly, Lanthanum nitrate(analytical reagent, AR), manganese nitrate (AR), strontium nitrate (AR) and cetyltrimethyl ammonium bromide(CTAB, AR) was used as starting materials. The LC-LSM sample was synthesized by dissolving 0.13 g strontium nitrate and 2.34 g Lanthanum nitrate in 100 mL distilled water, then adding 0.72 g manganese nitrate and 0.75 g CTAB with constant stirring. Then, the above solution was controlled to pH≈9 by adding the KOH solution with 0.1 mol L−1. The solution was transferred form the beaker into a Teflon container. The hydrothermal tank was heated to a temperature of 180 oC 5



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and kept the temperature for 2 hours. The deposit was washed by pure water and ethanol anhydrous ethanol for three times, respectively. Lastly, the resulting production was dried at the temperature of 80 oC for 24 hours, and calcined at the temperature of 500 oC for 2 hours. The LC material was synthesized by the similar method with LC-LSM hybrids except for the addition of Mn(NO3)2 and Sr(NO3)2. Scheme 1 shows the schematic illustration for preparing of the LC-LSM hybrid catalyst. The self-assembly of the surfactant molecules in reaction solution leads to the formation of micelles, which is used as the templates for the hybrid material synthesis process.

Scheme 1. Synthesis of the LC-LSM hybrid catalyst.

2.2 Sample characterization The formation phase of the different materials was studied by XRD (X-ray diffraction) with a Cu Kα radiation source from 20° to 80°. The different samples were observed by FESEM(Field emission scanning electron microscopy) and TEM (Transmission-electron-microscopy).

XPS

(X-ray

photoelectron

spectra,

hυ=1486.6 eV) of the different samples was investigated by a spectroscopy with Al-Kα radiation. All of the XPS spectra were calibrated by the C1s peak with the binding energy of 284.8 eV form the contamination. The specific surface area was investigated by nitrogen physisorption at 77K (ASAP 2020M, Micromertics 6


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Instrument Corp.). 2.3 Electrochemical evaluation The catalytic performances were tested with the rotating ring disk electrode device (RRDE). RRDE technique was performed by an electrochemical workstation. Pt wire and Hg/HgO electrode was used as counter electrode and reference electrode during the test process in a standard cell, respectively. The sample-coated RRD electrode (current collection efficiency: 37%; disk diameter of the glassy carbon is 5.6 mm, and the diameter of the Pt ring: 6.25~7.92 mm) was used as working electrode. All the tests were conducted in oxygen/nitrogen-saturated solution with 0.1 M KOH. Before the electrochemical measurements, the reference electrode was calibrated, which was E(RHE)=E(Hg/HgO)+0.923V.36 The potential of the disk on working electrode was scanned at the rate of 5 mV s−1 from 1.1 V to 0.1 V (vs. RHE), and the electrode of the Pt ring was held at 1.4 V. Oxygen gas was bubbled into electrolyte for thirty minutes to saturate the electrolyte, and O2-saturated atmosphere was maintained during testing. The CV (cyclic voltammetry) was investigated in O2/N2-saturated electrolyte. In addition, the stability of the different catalysts was studied by the chronoamperometry (CA) techniques at the constant voltage of 0.4 V for 10000 seconds. For catalyst inks, they were made by 10 mg catalyst, 10 mg Vulcan XC72, 2 mL alcohol and 160 μL Nafion solution (5wt%, Dupont). After that, the slurry was dispersed for thirty minutes using ultrasound equipment. Finally, 12.5 μL catalyst ink was dropped on RRD electrode, that it, the loading is 236 μg cm−2. The Pt/C slurry was prepared with 10 mg 20%Pt/C from the J.M. Company. 7



2.4 Battery performance The Al-air batteries using as-prepared samples as cathode catalysts were prepared for studying the electrochemical performance in a home-made testing house by a CT2001A testing system (Land Company). The fabrication procedures of Al-air batteries were described as follows.37 Air cathodes with a three-layer structure were fabricated. They contained current collector (CC), catalytic layer (CL) and gas diffusion layer (GDL). The GDL and CC with the size of 4 cm×4 cm was porous PTFE film and nickel foam, respectively. The air-breathing cathodes were fabricated as follow. The 0.5 g catalyst and 0.5 g Vulcan XC-72 was added in a beaker with 50ml ethanol; and the slurry was stirred by magnetic stirrer. 0.5 g PTFE emulsion solution (60 wt.% in water) was dripped into the mixture, and after that the slurry was stirred constantly to form a paste in an 80 oC water-bath. The catalyst paste was rolled into the conductive collector with a size of 2×2 cm2 and a thickness of 0.5 mm, sintered at 340 oC for thirty minutes. Lastly, the as-prepared samples were pressed onto a porous PTFE film at the temperature of 150 oC for two minutes. The batteries were studied in a self-made testing device. Aqueous solution of 4 mol L−1 KOH and pure Al-metal plate (>99.999%) was used as electrolyte and anode, respectively. 3.

RESULTS AND DISCUSSION Figure 1 shows the TEM and HRTEM photographs of the LC-LSM hybrid

material. The La2O2CO3 nano-rods with the size of ~15 nm are well scattered into the regular hexagonal LSM nano-sheets with the diagonal line being ~1 μm (Figure 1A and 1B). Figure 1C also shows the crystal structures of the 8


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La2O2CO3 nano-rod and LSM nano-sheet. Figure 1D shows the lattice parameters of the hybrid material determined by HRTEM. The interlayer spaces of 0.294 nm correspond to (103) plane of LC, while 0.385 nm correspond to (012) plane of LSM. This result indicates that LSM nucleation grows on the LC nano-rods, and then forms the regular hexagonal nano-sheet during the hydrothermal process. The elemental distribution of the composite material investigated by the EDS technique (Energy Dispersive Spectroscopy) also confirms that the nano-rods/nano-sheets are LC/LSM material (Figure 2). Accordingly, a strong interaction between LC nano-rods and LSM nano-sheets can be predicted for the hybrid catalyst.

Figure 1. TEM images (A, ×3k; B, ×12k; C, ×35k) and HRTEM images of the LC-LSM sample (D, ×250k; d1-inset, for nano-sheet; d2-inset, for nano-rod).

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Figure 2. EDS elemental distribution of the LC-LSM hybrid material.

The XRD patterns demonstrate the high crystallinity of La2O2CO3 and LSM in the hybrid material shown in Figure 3. The La2O2CO3 is indexed as the hexagonal (JCPDS No.84-1963), and the LSM is indexed as the perovskite (JCPDS No.51-0409) structures. The main peaks in XRD patterns (2θ= 23.1˚, 32.7˚, 32.9˚ and 58.3˚) of La0.7Sr0.3MnO3 belong to the (012), (110), (104) and (214) crystal planes of the perovskite phase, respectively; the peaks (2θ= 22.3˚, 25.2˚, 25.8˚, 27.6˚, 30.4˚, 44.4˚, 47.4˚ and 56.9˚) of the two samples correspond to (004), (100), (101), (102), (103), (110) and (116) crystal planes of the La2O2CO3 material, respectively. Moreover, the XPS results of LC-LSM hybrid clearly show the different peaks attributing to the La, Mn, Sr, and C elements. This result also confirms the formation of La2O2CO3 and LSM (show in Figure 4A). The specific surface area and the pore volume of the LC-LSM hybrid material are 6.3 m2 g−1 and 0.0314 cm3 g−1 (Figure S1, ESI†), respectively. The hybrid material exhibits type-III according to IUPAC standard using the isotherm of N2 adsorption/desorption. On the basis of the adsorption isotherm for the hybrid 10


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material, the pore size distribution is determined and shown in Figure S1. The mean pore diameter of the hybrid material is about 10 nm.

Figure 3. XRD results of the three samples.

Figure 4. XPS spectra of the full spectrum (A), the C 1s (B), Mn 2p (C), Mn 3s (D) and O ls spectra (E) of the LSM and LC-LSM catalysts. 11



Figure 5. Performances of the different samples toward ORR in O2-saturated electrolyte: (A) CV(dashed line for N2-saturated electrolyte), (B) polarization curves, (C) content of HO2− species, and (D) overall transferred electrons number (ne−). Scanning rate is 5 mV s−1; Pt-ring electrode is held at 1.4 V.

Figure 5A shows cyclic voltammetry (CV) curves of the five different catalysts. The peaks are negligible in N2-saturated electrolyte. There is obvious peaks display between 0.66 V and 0.78 V (vs. RHE) in O2-saturated electrolyte. From the figure, the LC-LSM hybrid catalyst exhibits the most positive peak at 0.78 V with 0.83 mA cm−2disk. It's remarkable that the significant increase of pseudocapacitive currents upon LC-LSM hybrid catalyst may be attributed to the high accessible specific surface area of the composite material, and/or the good conductivity of the composite material. It is well agreement with the 12


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previous results.24,38-40 Therefore, the promotion of the pseudocapacitance characteristics of the LC-LSM sample compared to either sample may be attributed to their efficient dispersion in the hybrid material. The catalytic activity of the LC-LSM hybrid material to ORR is also tested by the LSVs technique (linear sweeping voltammograms) and shown in Figure 5B. The onset potential (Eonset, the potential at −0.1 mA cm−2, Figure 4B-inset) and the half-wave potential (E1/2, the potential at j/2) of the LC-LSM composite is 0.927 V and 0.719 V, respectively. The results are much more positive than that of LC/LSM sample (0.888 V, 0.624 V), LC sample (0.840 V, 0.613 V) and LSM sample (0.868 V, 0.621 V). The Eonset of LC-LSM is also higher than those of the related materials, such as LaMnO3 (0.878 V)41, LaMnO3+δ (0.92 V)23,

(La0.7Sr0.3)0.98MnO3

(0.903

V)42,

Co-OEP/LSMF/C(0.906

V)43,

LaMn0.9Co0.1O3/NCNT (0.878 V)44 and La0.8Sr0.2Mn0.6Ni0.4O3 (0.868 V)45. The good onset potential of the LC-LSM hybrid material indicates that the sample has excellent intrinsic catalytic activity. There is general agreement that the current of the ring electrode is also an important indicator for evaluation of the catalytic performance of ORRCs. The ratio of the formed peroxides (XHO2― ) and the transferred electron numbers (ne−) during the RRDE testing can be acquired from the equation (1) and (2) with the ring current (Iring), the disk current (Idisk) and the ring collection efficiency (N).19, 46 XHO2― [%] = 100

2Iring N

Idisk +

Iring N

13


(1)


4N𝐼𝑑𝑖𝑠𝑘

𝑛𝑒 ― = 𝑁𝐼𝑑𝑖𝑠𝑘 + 𝐼𝑟𝑖𝑛𝑔

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(2)

It shows that the current density of the ring for LC-LSM hybrid material is much smaller than that of the others (Figure 5B), which implies that the hybrid material generates much less HO2− product during the reduction process (less than 3% when the potential is low than 0.9 V, shown in Figure 5C). The XHO2― of the five samples at 0.3 V and 0.6 V is summarized (Figure 5C-inset). The XHO2― of the LC-LSM composite sample is 0.8% at the potential of 0.3 V and 1.0% at the potential of 0.6 V, and even smaller than that of the commercial Pt/C sample (1.7% at 0.3 V, 1.3% at 0.6V). Figure 5D shows the relations of the electron transferred number (ne−) for the different samples with the scanning potential. It also can be seen that the ne− of LC-LSM is about 4 from 0.1 to 0.9 V, which is much larger than that of other samples. In addition, the ne− of the different catalysts were also summarized in Figure 5D (inset). The ne−of the LC-LSM sample at 0.3 V and 0.6V (vs. RHE) is 3.99 and 3.98, respectively, which is the highest among the five samples (including Pt/C sample). Figure 6A shows the polarization curves of LC-LSM sample at the different rotation rates. The transferred electron number of the LC-LSM sample also can be acquired by the equations (Equation 3 and 4). The results shown in Figure 6B further confirm that the reduction reaction mechanism on the LC-LSM hybrid material is an apparent 4e- reaction path. These above experiment results state clearly that the LC-LSM hybrid material has better electrocatalytic performance than other samples for ORR (Figure S2). The Koutecky-Levich equations (K-L equations) applied in this work are shown as 14


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follows:38 1/𝑖 = 1/𝑖𝐿 +1/𝑖𝐾 = 1/(𝐵𝜔1/2) + 1/𝑖𝐾

(3)

𝐵 = 0.62𝑛𝐹𝐶0(𝐷0)2/3𝜈 ―1/6

(4)

Where the current density of i is the practical measured values, the iL and the iK is diffusion-limiting current density value and kinetic current density value, respectively, the ω is rotation velocity (angular) of RRD electrode, n is the overall apparent transferred electron numbers, C0 is oxygen-gas volume concentration (1.2×10-6 mol cm-3), F is the constant value of 96485 C mol-1 (Faraday constant), D0 is the oxygen-gas diffusion coefficient (1.9×10-5 cm2 s-1, 0.1 M KOH), υ is 0.01 cm2 s-1 for the kinematic viscosity of the electrolyte.

Figure 6. Polarization curves (A) and K-L plots (B) of the LC-LSM hybrid material.

Figure 7A shows the Tafel slopes of the four different samples. The slopes, obtained from the Tafel equation, usually can be interpreted as the coverage degree of the oxygen species adsorbed on the surface of catalyst.20,

47-48

The

LC-LSM hybrid material shows the lowest slope (88 mV dec−1) among the four samples, even smaller than the value of Pt/C sample (95 mV dec−1). The result present that better performance may be attributed to the high adsorbed-oxygen 15



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coverage degree on surface of the LC-LSM composite material because of the efficiency interface contact between the LC and the LSM material. The mass specific activity of the ORR catalyst is obtained from the kinetic current (Ikinetic, shown in Figure 7B). The Ikinetic is calculated by the follow formula: Ikinetic=Ilim×Iobs/(Ilim-Iobs)

(5)

Ilim is the mass-transport limited current value; Iobs is the practical measured current value. The Ikinetics of LC-LSM at 0.7 V (30.4 mA mg−1oxide) is approximately 7.2 and 4.8 fold higher than that of LC (4.2 mA mg−1oxide) and LSM (6.3 mA mg−1oxide), respectively (Figure 7B inset). This result also indicates that LC nano-rods scattered inside in LSM nano-sheets is beneficial to theirs reaction activities to ORR process.

Figure 7. Electrochemical performances of the five samples: (A)Tafel curves and (B) specific activities.

The XPS results of the two catalysts are also shown in Figure 4. The records of C1s spectra for LSM and LC-LSM are also shown in Figure 4B. The major peak at 284.8 eV in LC-LSM sample matches the extensively delocalized alternate hydrocarbon. The main peaks of the C1s spectra centered at 286.1 eV and 288.4 eV are attributed to oxygen bound species of the C=O and C–O, respectively.49-51 The secondary strong peak at 289.4 eV in LC-LSM sample is characteristic of the CO32− form the La2O2CO3 material, whereas this peak is not observed in the pure LSM 16


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sample.34 In addition, the peak of C−O bonds for the C1s spectra in LC-LSM sample shows an obviously shift to high binding energy relative to the LSM sample, further confirm the strong interaction between the LC material and the LSM material in hybrid catalyst. From Figure 4C, the two peaks of the Mn 2p spectra centered at ~642 eV and ~653 eV are usually classified to the Mn 2p3/2 spectra and the Mn 2p1/2 spectra, respectively. Peak of the Mn 2p1/2 is generally separated into a high binding energy (BE) peak at 654.2 eV and a low BE peak at 652.5 eV. Meanwhile, the Mn 2p3/2 spectra are also divided into two main peaks centered at 641.2 eV and 642.7 eV. The peaks centered at 652.5 eV and 641.2 eV belong to Mn3+, 654.2 eV and 642.7 eV for Mn4+.42, 52-53 The content of Mn4+ increases from 28.8% in LSM sample to 55.1% for the LC-LSM hybrid material, while that of Mn3+ decreases from 71.2% to 44.9%. For further confirm the valence of Mn element in LC-LSM hybrid catalyst, the exchange splitting energy ΔE3s of the Mn 3s spectra was also studied (Figure 4D). The Mn oxidation state depends on the equation of VMn=9.67−(ΔE3s×1.27)/eV.54-56 From Figure 4D, the ΔE3s value of the LSM and LC-LSM sample is 5.11 eV and 4.54 eV, corresponding to Mn3.18+ and Mn3.90+, respectively. Comparing with LSM, the content of Mn4+ in LC-LSM is much higher, which also indicates that the interaction between the LC material and the LSM material in LC-LSM composite material. The O ls spectra are also shown in Figure 4E. Peak of the O 1s levels can be separated into three peaks centered at about 529.3 eV, 531.6 eV and 533.2 eV. They are usually corresponded to the oxygen in lattice (Olatt), adsorbed oxygen species on the surface 17



(Oads) and CO32− bonds in samples, respectively.34,

57-58

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The relative values of the

Oads/Olatt and CO32−/Olatt increases significantly from 0.46 (LSM) to 0.74 (LC-LSM), and 0.6 (LSM) to 1.64 (LC-LSM), respectively. For further investigation of the oxygen species adsorption behaviors on the catalyst surface, the valence band (VB) of the LSM and LC-LSM sample is studied and shown in Figure 8. The BE of 2 eV-5 eV can be attributed to the hybridized Mn3d-O2p states.59-64 In order to intuitively describe the difference between the LSM and LC-LSM sample, the ΔIntensity is calculated and shown in Figure 8B. From Figure 8B, there is a big difference between the two samples in the region of 2-5 eV. For LC-LSM hybrid catalyst, the ΔIntensity increases greatly at about 5 eV indicate that the hybridized bond of Mn–O in the composite material is significantly promoted.59 The above result states that the adsorption ability of oxygen species on the LC-LSM composite material is significantly enhanced.65 Interestingly, there is a notable difference compared with LSM sample at the VB tail states (shown in Figure 8A). According to previous studies, 49 the electron-withdrawing property of La2O2CO3 in LC-LSM hybrid material may be result in such band tails. This tendency can induce the VB edge broadening as a result of additional diffusive electronic states, which may be beneficial to the charge transfer during the ORR process. These above results from the XPS/XRD measurement and the electrochemical testing indicate that LC-LSM hybrid material can promote effectively the electrocatalytic activity of the LSM sample because of better interaction between LC and LSM in hybrid catalyst.

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Figure 8. Valence band (A) and ΔIntensity (B) of the LSM and LC-LSM catalysts.

The stability of LC-LSM hybrid material is also evaluated by the chronoamperometric technique at 1600 rpm for 90000 seconds in O2-saturated electrolyte (shown in Figure 9). From Figure 9A, the normalized current retention of the LC-LSM hybrid is 90.3% after 90000 seconds, exhibits better stability than the performance of 20%Pt/C sample (82.7%). In addition, the 𝒳HO2― value of the different samples obtained from the RRDE measurement is also collected during the testing. For LC-LSM, the 𝒳HO2― value increases slightly from 1.63% to 2.38% during the whole aging test. Whereas, the 𝒳HO2― value of the commercial Pt/C sample increases rapidly from 3.22 % to 48.68 % during the aging test. The E1/2 value of the LC-LSM is negative shift only 6 mV after the testing (Figure 9B and 9C), which is much smaller than that of 20%Pt/C sample (19 mV).

Figure 9. Durability and the 𝒳𝐻𝑂2― value of the different samples during the aging test (A), and LSV curves before and after the aging process (B and C). 19



Figure 10. The performances of the batteries using different materials as the cathode catalysts.

In order to further investigate the performance of LC-LSM hybrid catalyst, the batteries using LC, LSM, LC/LSM, LC-LSM and 20%Pt/C as the catalyst were studied (Figure 10). The Pmax of the battery using LC-LSM reaches 223.8 mW cm−2 which is the best one (except Pt/C sample). It is about 40% higher than the performance of the sample with LC as cathode catalyst (Pmax, 160.7 mW cm−2), and even superior to the battery using Pt/C as catalyst (213.3 mW cm−2). It is also better than the batteries using LSM (Pmax, 191.3 mW cm−2) and Fe-doped graphene-like carbon nanosheets (Pmax, 129.9 mW cm−2) as the ORRC, respectively.13,42 This can be ascribed to the good performance of the LC-LSM hybrid material to ORR. These above results further confirm that the LC-LSM hybrid prepared by hydrothermal method has high catalytic activity to ORR. 4.

CONCLUSIONS The LC-LSM composite catalyst was prepared by hydrothermal method. The 20


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La2O2CO3 nano-rods with the size of ~15 nm are well dispersed into regular hexagonal LSM nano-sheets with the diagonal line being ~1 μm. Due to the strong interaction between LC and LSM, LC-LSM has well catalytic activity and excellent durability. The Pmax of the battery using LC-LSM as the ORR catalyst in cathode electrode can reach 223.8 mW cm−2, which is about 40% higher than that of the LC sample. This work indicates that LC-LSM hybrid material can be used as a promising ORR electrocatalyst for metal-air battery. ASSOCIATED CONTENT Supporting Information Available: [N2 adsorption/desorption isotherm of the LC-LSM hybrid catalyst, and the pore size distribution obtained on the basis of the adsorption isotherm. The LSV curves and the Koutecky-Levich plots of the different samples.] AUTHOR INFORMATION Corresponding Author *E-mail:[email protected](Y. X.) *E-mail: [email protected] (Z. L.) ORCID Yejian Xue: 0000-0002-3943-8953 Zhaoping Liu: 0000-0003-1770-4605 Notes The authors declare no competing financial interest. 21



ACKNOWLEDGEMENTS Author Xue Yejian received funding from Ningbo Natural Science Foundation (2018A610015). Author Liu zhaoping received funding from National Key Research and Development Program of China (2016YFB0100100) and Key Research Program of the Chinese Academy of Sciences (KGZD-EW-T08). REFERENCES 1. Cheng, F.; Chen, J., Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts. Chemical Society Reviews 2012, 41, 2172−2192. 2. Li, Y.; Dai, H., Recent advances in zinc-air batteries. Chemical Society Reviews 2014, 43, 5257−5275. 3. Mokhtar, M.; Talib, M. Z. M.; Majlan, E. H.; Tasirin, S. M.; Ramli, W. M. F. W.; Daud, W. R. W.; Sahari, J., Recent developments in materials for aluminum–air batteries: A review. Journal of Industrial and Engineering Chemistry 2015, 32, 1−20. 4. Xue, Y.; Sun, S.; Wang, Q.; Dong, Z.; Liu, Z., Transition metal oxide-based oxygen reduction reaction electrocatalysts for energy conversion systems with aqueous electrolytes. Journal of Materials Chemistry A 2018, 6, 10595−10626. 5. Xu, S.; Li, Z.; Ji, Y.; Wang, S.; Yin, X.; Wang, Y., A novel cathode catalyst for aluminum-air fuel cells: Activity and durability of polytetraphenylporphyrin iron (II) absorbed on carbon black. International Journal of Hydrogen Energy 2014, 39, 20171−20182. 6. Li, J.; Chen, J.; Wang, H.; Ren, Y.; Liu, K.; Tang, Y.; Shao, M., Fe/N co-doped carbon materials with controllable structure as highly efficient electrocatalysts for oxygen reduction reaction in Al-air batteries. Energy Storage Materials 2017, 8, 49−58. 7. Li, J.; Chen, J.; Wan, H.; Xiao, J.; Tang, Y.; Liu, M.; Wang H., Boosting oxygen reduction activity of Fe-N-C by partial copper substitution to iron in Al-air batteries, Applied Catalysis B: Environmental 2019, 242,209−217. 8. Armand, M.; Tarascon, J. M., Building better batteries. Nature 2008, 451, 652−657. 9. Stoerzinger, K. A.; Lü, W.; Li, C.; Ariando; Venkatesan, T.; Shao-Horn, Y., Highly Active Epitaxial La1–xSrxMnO3Surfaces for the Oxygen Reduction Reaction: Role of Charge Transfer. The Journal of Physical Chemistry Letters 2015, 6, 1435−1440. 10. Li, T.; Liu, J.; Jin, X.; Wang, F.; Song, Y., Composition-dependent electro-catalytic activities of covalent carbon-LaMnO3 hybrids as synergistic catalysts for oxygen reduction reaction. Electrochimica Acta 2016, 198, 115−126. 11. Liu, K.; Huang, X.; Wang, H.; Li, F.; Tang, Y.; Li, J.; Shao, M., Co3O4-CeO2/C as a Highly Active Electrocatalyst for Oxygen Reduction Reaction in Al-Air Batteries. ACS Applied Materials Interfaces 2016, 8, 34422−34430. 22


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Table of Contents Graphics

A nano-architectured La2O2CO3-La0.7Sr0.3MnO3 hybrid catalyst is synthesized by a facile one-pot method.

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Perovskite Hybrid Material as

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