Journal of Colloid and Interface Science 630 (2023) 269–280

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Journal of Colloid and Interface Science

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

Metal oxide Perovskite-Carbon composites as electrocatalysts for zinc-

air batteries. Optimization of ball-milling mixing parameters
M. García-Rodríguez a, J.X. Flores-Lasluisa a, D. Cazorla-Amorós b, E. Morallón a,⁄
a
Dept. Química Física e Instituto Universitario de Materiales, Universidad de Alicante, Ap. 99, E-03080 Alicante, Spain
b
Dept. Química Inorgánica e Instituto Universitario de Materiales, Universidad de Alicante, Ap. 99, E-03080 Alicante, Spain

g r a p h i c a l a b s t r a c t

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

Article history: Zn-air batteries (ZABs) are promising electrochemical devices to store energy. Metal oxide perovskites
Received 26 July 2022 mixed with carbon materials are highlighted as interesting materials for this application because of their
Revised 3 October 2022 appropriate bifunctional performance in oxygen reduction reaction (ORR) and oxygen evolution reaction
Accepted 16 October 2022
(OER). The interaction between both components of the electrocatalyst is important in the bifunctional
Available online 20 October 2022
electrocatalytic activity, and the mixing method plays an important role in this interaction. Then, different
mixing methods have been studied in this work (ball-milling, mortar and manual shaking). The use of dif-
Keywords:
ferent physicochemical techniques such as temperature programmed desorption (TPD), temperature pro-
Metal oxide perovskite
Perovskite-Carbon composite
grammed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) in the materials characterization,
Zn-air battery allows us to conclude that the mixing method strongly influences the particle size and the interaction
ORR between both components, which determine the final electrocatalytic activity. The materials prepared
OER by ball-milling displayed the best performance. Herein, the experimental conditions were optimized to
Bifunctional catalyst obtain electrocatalysts with enhanced electrocatalytic activity for ORR and OER. Low rotating speed, air
Ball-milling atmosphere and low ball-milling time generate electrocatalysts with a small nanoparticle size, more homo-
geneous and with a higher interaction between both components, which enhances electron transfer, and
consequently, the overall oxygen-involved reactions. The best electrocatalyst obtained was studied as

⁄ Corresponding author.

https://doi.org/10.1016/j.jcis.2022.10.086
0021-9797/Ó 2022 The Authors. Published by Elsevier Inc.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
M. García-Rodríguez, J.X. Flores-Lasluisa, D. Cazorla-Amorós et al. Journal of Colloid and Interface Science 630 (2023) 269–280

air-electrode in a Zn-air battery and it was compared to a commercial Pt/C electrocatalyst, obtaining higher
cyclability (55.2 vs 51.7 %) for 30 h, and higher energy density at 5 mA/cm2 (764 mAh/g vs 741 mAh/g).
Ó 2022 The Authors. Published by Elsevier Inc. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction the carbon material through the use of a mortar [26], electrospin-
ning [27], chemical vapor deposition [28] or ball-milling [29],
The use of fossil fuels has increased greenhouse gas emissions, among others. The ball-milling treatment (mechanochemical
making climate change a pressing issue for mankind. The use of approach) stands out among the others because of its simplicity
renewable energy sources to replace fossil fuels is one of the most and ease of extrapolation from the lab to industry, which is
important challenges to alleviate climate change [1,2]. However, unachievable with other methods. This method involves placing
these are discontinuous primary energy sources, making the use the different components to be mixed into a vessel that contains
of energy storage devices necessary for their successful deploy- balls of inert material and then rotating the vessel to enhance
ment. Electrochemical energy storage devices are one of the most the contact between the phases. Time, rotation speed and the
interesting for this purpose and they will become critical compo- atmosphere used are important variables that may be controlled
nents of the future energy network to help store and deliver [30]. Depending on the mechanical energy, elastic or plastic defor-
renewable energy [3]. mation can be achieved [31]. If the mechanical energy is not high
Among the different electrochemical energy storage devices, enough, the kinetic energy transferred to the reagents only pro-
metal-air batteries (MEBs) are highlighted as interesting devices vides energy to reduce the size of the particles. However, if the
that store and deliver energy through redox reactions between energy is high enough, the reactants can be chemically modified
the metal and oxygen. These batteries are growing in popularity through the cleavage of chemical bonds [32]. This leads to the for-
due to their higher energy densities than conventional lead-acid mation of new bonds between reactants and, consequently, the
batteries, nickel-metal hydride batteries, and lithium-ion batteries formation of new materials with significantly different chemical
[4]. Although lithium, zinc, aluminum, sodium, and other metal properties. Then, the ball-milling method can play an important
electrode materials have been extensively studied, the zinc elec- role in modulating the interaction between the carbon material
trode is the best choice for aqueous electrolytes due to its strong and the metal oxide perovskite.
corrosion resistance in alkaline solutions, low cost and large In this work, we propose the synthesis of composites that con-
reserves, making Zn-air batteries (ZABs) a very promising energy sist of a Co-doped LaMnO3 perovskite mixed with a carbon black
storage device [5–8]. material for electrochemical oxygen reactions (ORR and OER) using
Sluggish kinetics and high overpotentials of the electrochemical different mixing methods. Co-doped LaMnO3 perovskites were pre-
oxygen reduction reaction (ORR) and oxygen evolution reaction viously studied for both ORR and OER [18]. The results showed that
(OER) are one of the important hurdles for the implementation of a low Co content favors the presence of surface Mn4+, which
efficient fuel cells and metal-air batteries [9–11]. Although noble increases the catalytic activity. However, if Co is added in larger
metal-based materials are the most effective ORR/OER electrocata- amounts, changes in crystal structure and particle size occur that
lysts, the high cost and scarcity of precious noble metals, as well as negatively affect the catalytic activity. In this study LaMn0.7Co0.3O3
the non-efficient bifunctionality against the target reactions, have perovskite has been selected since it has an outstanding activity
prompted scientists to look for more efficient and highly stable towards both ORR and OER. Therefore, the main objective of this
non-noble metal-based electrocatalysts [12–14]. work is to compare different methods of materials mixing (ball-
The family of perovskite-type metal oxides AMO3, in which A is mill, mortar, and manual shaking) to investigate their influence
a rare-earth or alkaline earth element and M is a transition metal, on the electrochemical activity. We also provide an optimization
are attractive candidates for ORR/OER bifunctional reactions. This of the ball-milling experimental parameters. The physicochemical
is due to their structural stability and their ability to substitute ele- and electrochemical properties of the different composites have
ments of varying valence, electronegativity or ionic size at the A been analyzed and their performance in a ZAB has been assessed.
and M sites, that permits tuning the structural, physical and elec-
tronic properties of the electrocatalyst [15,16]. However, because
of the lack of proper electrical conductivity, the catalytic activity 2. Experimental
of these metal oxides is limited. One alternative to increase the
electrical conductivity is to introduce a second phase with higher 2.1. Materials and reagents
electron conductivity, such as carbon materials. Therefore, metal
oxide Perovskite-Carbon material composites have been proposed Reagents used were Vulcan XC-72R carbon black (Vulcan)
as potential replacement for noble metal-based materials [17–20]. (Cabot Corporation), potassium hydroxide (KOH) (VWR Chemicals,
According to several studies, the improved OER/ORR activity of a 85 %), ethanol (C2H5OH) (Alfa Aesar, 99.5 %) isopropanol (Acros,
hybrid electrocatalyst made up of a carbon material and a Organics, 99.5 %), NafionÒ 5 % w/w, 1-propanol (C3H8O) (Alfa Aesar,
perovskite-type metal oxide is mostly due to the synergistic 99.9 %), 20 wt% Pt/C (Sigma-Aldrich, 98 %), lanthanum(III) nitrate
impact of the components. The synergistic effect might be associ- hexahydrate (La(NO3)3
6H2O) (Sigma Aldrich, 99.9 %), manganese
ated with the formation of an interfacial structure which is respon- (II) nitrate tetrahydrate (Mn(NO3)2
4H2O) (Alfa Aesar, 99. 98 %),
sible for the enhancement of the electrocatalytic activity over cobalt(II) nitrate hexahydrate (Co(NO3)2
6H2O) (Sigma Aldrich,
those of individual components. The role of the carbon material 99.9 %), zinc acetate dihydrate (Zn(O2CCH3)2
2H2O) (Sigma
acting as a co-catalyst can also contribute to this effect. According Aldrich, 98 %), hexadecyltrimethylammonium bromide (CTAB)
to the literature, these composites can be synthesized in several (CH3(CH2)15N(Br)(CH3)3 (Sigma Aldrich, 99.9 %), and Zn foil
ways [21]. The most common approach is to first synthesize the (ThermoScientific, 99.98 %). The solutions were prepared in ultra-
metal oxide, which may be achieved by co-precipitation [22], pure water (18 MX cm, MilliporeÒ Milli-QÒ water). Gases, N2
sol–gel [23], hydrothermal [24] or microwave procedures [25]. (99.999 %), O2 (99.995 %), H2 (99.999 %) and synthetic air were pro-
Subsequently, the metal oxide perovskite can be combined with vided by Carburos Metálicos and used without any pretreatment.
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2.2. Synthesis procedure (VG Scientific, Sussex, UK) equipped with a hemispherical electron
analyzer with nine channeltrons (passing energy of 2–200 eV) and
2.2.1. Perovskite-type metal oxide hydrothermal synthesis an X-ray source with Al radiation (Ka 1253.6 eV). The bond energy
The hydrothermal synthesis method used to prepare the of the C1s peak at 286.4 eV was taken as an internal standard. The
LaMn0.7Co0.3O3 (LMCO) perovskite was modified with respect to XPS data were deconvoluted using the XPSPEAK41 program; the
that found in the literature for LaMnO3 [33]. In the first step, the experimental curves were fitted using Lorentz-Gaussian functions,
metal precursors were mixed in water in stoichiometric ratios and the background was a Shirley line. The XPS data were obtained
(Co is introduced in a 30 % of the Mn quantity), and the surfactant from the average of seven cycles; the estimation of the uncertainty
CTAB was added in a 1:50 M ratio to the metal content. Then, drops of the XPS measurements is ±5 %.
of 6 M KOH were added until pH  14 was reached, and the solu- Temperature programmed desorption (TPD) studies were per-
tion was stirred for 18 h. The solution was then transferred to a formed by heating carbon-containing samples (approximately
Teflon reactor and introduced into an autoclave, which was heated 10 mg) from 120 to 940 °C at a heating rate of 20 °C/min under a
at 180 °C for 48 h in an oven. Afterward, the autoclave was cooled helium flow rate of 100 mL/min. These experiments were per-
in an ice bath. Then, the material was washed, filtered and dried at formed in a thermogravimetric system (TA Instruments, SDT
100 °C. Finally, the sample was calcined at 700 °C for 7 h under air Q600 Simultaneous) coupled to a mass spectrometer (PRISMA
atmosphere and the perovskite-type metal oxide LMCO was PRO QMG 250 M1). The quantity of CO evolved was measured
obtained. using the 28 m/z line. The mass spectrometer was calibrated using
calcium oxalate and the uncertainty of the measurements is ±5 %.
2.2.2. Metal oxide Perovskite-Carbon material composite Perovskite-Carbon composites were also analyzed by tempera-
The as-obtained metal oxides were mixed with Vulcan by ture programmed reduction (TPR, 5 vol% H2 in Ar (35 mL/min),
employing different methods to obtain the Perovskite-Carbon 10 °C/min up to 950 °C) using a Micromeritics Pulse Chemisorb
composites. In the ball-milling (BM) approach, a Retsch PM 200 2705 equipment with a thermal conductivity detector (Norcross,
planetary ball-mill equipment was used with different milling con- GA, USA). The uncertainty of the measurement is ±3 %, determined
ditions such as time (30, 60, 180 min), atmosphere (Ar and air) and from comparison with other samples.
milling speed (350 and 500 rpm). In all of them, 0.5 g of perovskite Sample morphologies were characterized by transmission elec-
together with 0.5 g of Vulcan and 10 agate balls of 9.91 mm in tron microscopy (TEM, JEOL-2010, 200 kV) and scanning electron
diameter were mixed in the 50 mL agate ball-mill vessel, leading microscopy (SEM, JEOL, 0.5–30 kV).
to a ball-to-powder weight ratio of 14–1. The samples were named The study of the electrocatalytic activity was performed in an
as BM_time_rotation speed_atmosphere. For milling in Ar atmo- Autolab PGSTAT302 potentiostat (Metrohm, Netherlands) with an
sphere, the ball-mill vessel was introduced into a glove box (VAC error in the measured current of ±0.2 %. The working electrode
Nexus Model, California, USA), filled with high purity Ar, for 24 h was a rotating ring-disk electrode (RRDE) (Pine Research Instru-
to ensure air removal, and it was sealed inside the box. Physical ments, USA) with a glassy carbon disk electrode (5.61 mm in diam-
mixing by mortar was conducted in an agate mortar by mixing eter) and an attached platinum ring, the counter electrode was
20 mg of metal oxide perovskite with 20 mg of Vulcan and grinding graphite, and the reference electrode was a reversible hydrogen
for 15 min (mortar sample). And finally, manual shaking was per- electrode (RHE) immersed in the working electrolyte through a
formed by mixing 5 mg of perovskite and 5 mg of Vulcan in a vial Luggin capillary.
and shaking manually for 15 min (manual shaking sample). Before electrochemical characterization, a catalytic ink was pre-
pared by sonicating a suspension containing 1 mg of Perovskite-
2.3. Characterization techniques Carbon composites and 1 mL of a solution composed of 0.02 vol%
NafionÒ and 20 vol% isopropanol in water. Then, 120 ll of the dis-
Composites were characterized by X-ray diffraction (XRD) using persion were deposited on the glassy carbon disk. The electro-
a Cu a Ka radiation source at a step of 0.05° in the 2h range from chemical characterization was performed by cyclic voltammetry
10° to 80° on a Bruker D8-Advance diffractometer (Billerica, USA) in N2 saturated atmosphere in 0.1 M KOH at a scan rate of
with a Goebel mirror (non-planar samples) and an X-ray generator 50 mV/s. Electrocatalytic activity towards the ORR was studied
KRISTALLOFLEX K 760-80F (power: 3000 W, voltage: 20–60 kV and by linear sweep voltammetry (LSV) in an O2 saturated 0.1 M KOH
current: 5–80 mA). The crystallite size was estimated by applying solution between 1.0 and 0.0 V (vs RHE) at different rotation rates,
the Scherrer equation (Eq. (1)) [34]: from 400 to 2025 rpm, and at a scan rate of 5 mV/s. Throughout all
experiments, the potential of the Pt ring electrode was kept con-
kk stant at 1.5 V (vs RHE). The hydrogen peroxide formed on the disk
Dc ¼ ð1Þ
bcosðhÞ electrode is oxidized on the Pt ring electrode. Then, the electron
transfer number was determined from the current of the disk
where Dc is the crystallite size (nm); k is the constant related to the and the ring electrodes as follows (Eq. (3)):
shape of the grain, whose value is 0.89; k is the wavelength of the
radiation source used, which is 0.15406 nm; b corresponds to the
full width at half maximum (FWHM) (radians), and h is the Bragg
angle. To subtract the instrumental broadening factor from the 4Ir
measured FWHM value, a crystalline quartz pattern was used. The ne ¼ ð3Þ
Id þ Ir =N
corrected FWHM value of the sample was calculated according to
the following equation [34]:

b2real ¼ b2obs  b2inst ð2Þ

where Ir and Id are the currents measured in the ring and the disk
where breal is the value obtained from the contribution of the crys- electrodes, respectively, and N is the efficiency of ring collection,
tallite size, bobs is the measured value, and binst is the broadening which was determined to be 0.37. The OER experiments were per-
related to the instrument. formed using RRDE and LSVs from 1 to 1.8 V (vs RHE) in the N2 sat-
X-ray photoelectron spectroscopy (XPS) experiments were per- urated atmosphere at a rotation rate of 1600 rpm at 5 mV/s in 0.1 M
formed in a VG-Microtech Multilab 3000 electron spectrometer KOH.
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2.4. Zn-air battery compensation mechanisms that perovskite metal oxide can suffer
due to Co substitution. It seems that the peak corresponding to
The zinc-air battery (ZAB) was tested using the instrumentation plane (0 1 1) is broader when using ball-milling and that, in some
shown in Fig. S1. As air electrode (positive electrode), the cases, the peak splits into two signals, which may be related to
BM_30_350_O2 catalyst, or the commercial 20 wt% Pt/C catalyst the transformation of the cubic phase to the rhombohedral phase
ink (5 % NafionÒ in isopropanol), was uniformly brush painted on [23].
the carbon paper (QUINTECH, Freudenberg H23C6) until a mass The XRD for the manually shaken sample contains low crys-
loading of 1.3 mg/cm2 was reached. The negative electrode was a tallinity peaks (Fig. 1A), showing the typical peaks of an amor-
polished Zn foil and the electrolyte was an aqueous solution of phous carbon material [35], which seem to hide the contribution
6 M KOH + 0.2 M Zn(O2CCH3)2. The geometrical area of the elec- of perovskite metal oxide. Therefore, the diffractogram of the man-
trodes was 2.8 cm2. Battery tests were performed using an ARBIN ually shaken sample confirms its heterogeneity. This is the first evi-
multi-channel SCTS battery testing potentiostat and the error of dence that the mixing process is critical to produce homogenous
the registered currents is ±0.02 %. Polarization curves were per- electrocatalysts.
formed at a rate of 1 mA/s. In each 10 min cycle, galvanostatic dis- The crystallographic information obtained from XRD is summa-
charge and charge cycles were performed at a constant current rized in Table 1. A crystallite size of 57 nm is obtained for the
density of 1 mA/cm2. In the stability experiment, the electrolyte BM_180_350_O2 sample, which is larger than that for the
was recirculated with a peristaltic pump. BM_30_350_O2 sample, with 30 min of ball-milling (43 nm).
Although increasing ball-milling times may produce a lower crys-
tal size, it seems that high ball-milling times may favor an increase
3. Results and discussion in the crystal size. This should be a consequence of the high energy
produced in the ball-milling process, which can promote nanopar-
3.1. Crystal structure characterization by XRD ticle sintering and a change in the crystalline phase. Additionally,
the ball-milling treatment produces smaller crystal sizes than the
Since the crystal structure influences the electrocatalytic activ- mortar (59 nm), except for the sample ball-milled in air and for
ity of the perovskite-type metal oxide toward the electrochemical the longer times. On the other hand, the crystallographic parame-
oxygen reactions, characterization of the structure by X-ray ters are not significantly affected by the speed or atmosphere of the
diffraction is necessary. Fig. 1A displays the XRD diffractograms ball-milling (Table 1). Finally, the cell parameters have not signifi-
of the Perovskite-Carbon composites, showing peaks at 2h = 23, cantly changed as a result of the mixing strategy used, and they
33, 40, 47, 58, and 68 ° in the ball-milled and mortar-treated sam- agree with crystallographic databases.
ples, which correspond to the planes (0 1 0), (0 1 1), (1 1 1), (0 2 0),
(1 2 1), (0 2 2), respectively. These XRD peaks are characteristic of
the cubic LaMnO3 phase and the Pm3m space group (ICDD 01- 3.2. Morphological characterization
075-0440). Fig. S2 depicts a typical unit cell. It should be empha-
sized that the structure of LaMnO3 is preserved in LMCO perovskite Fig. 2 shows the TEM images of the different Perosvkite-Carbon
because the amount of Co in its structure is insufficient to change materials. It can be observed that the ball-milling method pro-
it; this observation is consistent with previous studies [23]. In the duces a better distribution of both the carbon material and the per-
doping process, charge transfer processes will occur, leading to ovskite metal oxides, and agglomerated particles of sizes between
changes in the oxidation state of the cations and the possible gen- 0.1 and 10 lm are formed, that contain both components homoge-
eration of oxygen vacancies. Fig. S2 shows a diagram of the charge nously distributed (Fig. 2A and B). The observed particle size is

Fig. 1. XRD patterns of LMCO-Vulcan composites relative to LaMnO3 ICDD reference.

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Table 1 200 nm with irregular shapes. However, no clear differences can

Average crystallite size and lattice parameters for Perovskite-Carbon composites be appreciated with this technique for the different mixing meth-
obtained from XRD patterns in Fig. 1.
ods because the particle size of the metal oxide particles are not
Sample a (Å) V (Å3) Dc (nm) very different.
BM_30_350_O2 3.83 56.16 43
BM_60_350_O2 3.83 56.27 41
BM_180_350_O2 3.84 56.70 57 3.3. Characterization by XPS
BM_30_500_O2 3.83 56.26 39
BM_30_350_Ar 3.83 56.20 41
Surface characterization of the composites is important to dis-
BM_180_350_Ar 3.83 56.08 47
BM_30_500_Ar 3.83 56.14 42 tinguish the different species formed and oxidation states of the
Mortar LaMnO3* 3.83 56.38 59 different atoms, especially the B-site cations, which play a signifi-
3.88 58.41 - cant role in the electrochemical reactions [36]. An XPS study of the
*
JCPS-International Center for Diffraction.
elements La 3d, Mn 2p, and O 1 s was performed for the different
samples to assess the ion oxidation states. Co 2p spectrum of the
pristine LMCO (Fig. S3) and Table S1 show that Co has been incor-
porated into the metal oxide. The Co 2p spectrum of the composite
characteristic of this type of electrocatalysts [23]. It is worth noting is shown in Fig. S4; however, the signal is weak and noisy due to
that, in the case of the samples prepared by manual shaking and the low Co concentration. The signals of the metallic elements
using a mortar, there is a clear separation between both compo- appear at higher binding energies in Perovskite-Carbon composites
nents (Fig. 2C and D), what demonstrates the higher heterogeneity than in pristine perovskite metal oxides. This is due to a change in
achieved by these mixing methods. the chemical environment caused by the carbon material: since
The SEM images (Fig. 3) show the presence of particles that are carbon atoms have a higher electronegativity, they withdraw elec-
formed by agglomeration of nanoparticles between 100 and tronic density from the perovskite, which increases the electron

Fig. 2. TEM images of the Perovskite-Carbon material composites of the samples (A) BM_350_30_O2, (B) BM_350_30_Ar, (C) Mortar, (D) Manual shaking.

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Fig. 3. SEM images of the Perovskite-Carbon material composites of the samples (A) BM_350_30_O2, (B) BM_350_30_Ar, (C) Mortar, (D) Manual shaking.

The two pristine components have different XPS spectra compared

to the Perovskite-Carbon composites both in shape and amount of
oxygen. However, the Perovskite-Carbon composites show similar
amounts of oxygen although the percentage of each oxygen species
changes what, can be due to the differences in the preparation
method. In the Perovskite-Carbon composites five peaks can be
detected in the XPS spectra of O 1s: two related to the metal oxide
perovskite, two related to the carbon material, and the fifth one
related to the MAOAC species, where M is the perovskite metal.
This last species is attributed to the interaction between the carbon
material and the perovskite metal oxide. The peak at 529 eV and
that at around 531 eV can be attributed to lattice oxygen species
(O2–) and surface-adsorbed oxygen (O-, O2–, or O2– 2 ) in perovskite
metal oxide, respectively, and the peak at around 533 eV can be
associated with the MAOAC species [16,37,38]. Then, this peak
can be used as a measurement of the degree of interaction between
the carbon material and the metal oxide [18].
The contributions of the different oxygen species are shown in
Table 2. The significant difference is that the MAOAC species are
present in larger ratios (more than 12 %) in the ball-milled samples,
revealing the enhanced contact between the perovskite and the
Fig. 4. O 1s XPS deconvolution spectra. The purple peak represents the contribution
of the MAOAC interaction. (For interpretation of the references to colour in this carbon material. It must be noted that, as previously observed
figure legend, the reader is referred to the web version of this article.) [18], the mortar treatment also results in the formation of the
MAOAC peak although with a lower intensity (9%), thus showing
binding energy [21]. The mixing procedure does not affect the oxi- that the energy is high enough to generate this interfacial interac-
dation state of La 3d (Fig. S5) and Mn 2p (Fig. S6) cations, with La in tion. Furthermore, the contribution of these species is not observed
its trivalent form and Mn as a mixture of oxidation states Mn(III)/ in the manually shaken sample, which indicates the low interac-
Mn(IV), in agreement with previous studies [23]. tion between the two components of the composite.
Fig. 4 shows the XPS of O 1s for the Vulcan, the LMCO metal The effect of ball-milling time and the atmosphere on the car-
oxide perovskite and the mixed Perovskite-Carbon composites. bon material have also been investigated by XPS. For this purpose,

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Table 2
Contributions of each peak of the O1s deconvolution as a percentage of total contributions.

Sample Percentage (%)

O2– (lat) O (ads) CAO C@O MAOAC
BM_30_350_Ar 18.0 7.3 45.6 16.8 12.3
BM_30_350_O2 23.6 12.3 35.1 13.0 16.0
Mortar 19.5 7.7 47.0 17.2 8.6
Manual shaking 17.6 – 51.0 31.4 –

Vulcan without the presence of perovskite, was ball-milled at Table 3

times of 30 and 180 min and in O2 and Ar atmospheres. Fig. S7 CO desorption values from the TPD technique for the different samples. In the case of
the Perovskite-Carbon composites, the amounts desorbed are referred to the amount
shows two peaks associated with C@O (532.3 eV) and CAO
of perovskite metal oxide.
(533.6 eV) species [39]. At 180 min, the contribution from CAO
species decreases mainly when the ball-milling is done in Ar atmo- Sample lmol CO (g1)
sphere. This decrease may affect the interaction with the per- BM_30_350_O2 4230
ovskite metal oxide when the milling is performed with the BM_60_350_O2 4200
BM_180_350_O2 3120
mixture of the two components, thus resulting in a lower number
BM_30_500_O2 4050
of MAOAC species, in agreement with the experimental results BM_30_350_Ar 4120
(Table 2). When comparing the oxygen content for the perovskite BM_180_350_Ar 2400
component in the composites (i.e., O2– (lat), O (ads) in Table 2), BM_30_500_Ar 4440
some increase in these contributions is observed when the ball Mortar 800
Manual shaking 410
milling is done in air atmosphere, which is accompanied by a Vulcan 190
decrease in the O content for the C@O and CAO species (compare Theoretical oxygen in LaMn0.7Co0.3O3 12300
data in Table 2 for samples BM_30_350_O2 and BM_30_350_Ar).
This suggest that in air atmosphere there is a more efficient oxygen
transfer from the carbon material to the metal oxide. face oxygen groups in this material. The TPD for the material
prepared by manual shaking has almost no difference with that
of Vulcan, indicating that the observed gas desorption is essentially
3.4. Characterization by TPD
that from the carbon material. Interestingly, the TPD profiles are
quite different for the rest of the Perovskite-Carbon composites,
Fig. 5 shows the CO evolution during the heat treatment for the
being significantly different in shape and amount of gas desorbed
different electrocatalysts and the carbon material (Vulcan). Table 3
for the materials prepared by ball-milling. In all the cases, the
includes the quantification of the CO evolved from the TPD exper-
amount of CO desorbed increases compared to the Vulcan and
iments for the different samples. No significant amounts of CO2 or
manually shaken Perovskite-Carbon samples. This increase must
O2 were detected during the TPD experiments, thus the total
be due to the interaction between the metal oxide and the carbon
amount of desorbed O corresponds to the amount of desorbed
material that produces the carbothermal reduction of the metal
CO. Since no O2 is detected in the TPD, it can be concluded that
oxide at the interphase during heat treatment. This observation
the perovskite metal oxide does not decompose in this range of
is in good agreement with the XPS results. It is expected that the
temperatures, producing dioxygen evolution.
higher the strength and degree of the interaction (i.e., formation
The TPD profile for Vulcan carbon material shows a small CO
of MAOAC species), the higher the CO evolution will be. Thus,
evolution that comes from the decomposition of CO-type func-
the evolution of CO can be used as a measurement of the extent
tional groups. This desorption agrees with the low number of sur-
of the Perovskite-Carbon interphase and its strength. Table 3
includes the quantification of CO desorbed from each material. It
also includes the theoretical amount of O that contains the per-
ovskite metal oxide under study.
In this sense, the material obtained with the mortar exhibits a
higher CO evolution than the Vulcan material, but the amount des-
orbed is much lower than for ball-milled samples. Among the ball-
milled samples, it can also be observed that there are important
differences depending on the ball-milling conditions. The ball-
milling speed seems to have a minor effect on the TPD compared
to the effect of the ball-milling time. As a result, compared to the
other ball-milled samples, the CO desorption is substantially lower
in the samples prepared at 350 rpm for a long milling period (i.e.,
180 min). This decrease can be related to the increase in particle
size detected by XRD, since a higher crystal size in the nanoparti-
cles will correspond to a lower Perovskite-Carbon interphase. For
the lowest ball-milling time studied (i.e., 30 min), the amount of
CO desorbed is high for the two atmospheres used, although the
highest amounts and the lowest desorption temperatures are
obtained for the materials ball-milled in air. Since this is an oxidiz-
ing atmosphere, it is expected that it will favor the formation of
higher amounts of MAOAC species. The lower desorption temper-
Fig. 5. CO-TPD profiles for the samples that were prepared at different ball-milling atures observed, but similar profiles, suggest that the species
conditions and mixing methods.

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M. García-Rodríguez, J.X. Flores-Lasluisa, D. Cazorla-Amorós et al. Journal of Colloid and Interface Science 630 (2023) 269–280

formed are less stable than those generated under the Ar atmo- with the TPD and XPS results and with the MAOAC interaction
sphere, probably because a higher surface concentration of which is promoted by ball-milling.
MAOAC species can produce some species destabilization due to
repulsive interactions. However, this is an issue that needs further
research. In these materials prepared with a ball-milling time of 3.6. Electrocatalytic activity to ORR and OER
30 min, more than 30 % of the oxygen contained in the perovskite
metal-oxide reacts with the carbon material, showing that the The methods employed for mixing the perovskite and carbon
extent of the interaction reached is high using this experimental materials produced composites with different physicochemical
methodology. properties; thus, the preparation method is expected to affect the
electrochemical properties, and consequently, the electrocatalytic
activity. Electrochemical characterization was performed by cyclic
voltammetry in 0.1 M KOH in a N2 saturated atmosphere. Fig. S9
3.5. Characterization by TPR shows the cyclic voltammograms of the different materials in
which the redox processes at 0.5–0.8 V (anodic sweep) and 0.3–
To deepen into the interaction between the metal oxide and the 0.7 V (cathodic sweep) associated with the redox Mn(III)/Mn(II)
carbon material, TPR technique has been used. This is a widely reaction are clearly observed [18,44]. It can be noticed that the
used technique to analyze the reducibility of metal oxides and dif- mixing method produces changes in the voltametric charge, which
ferent catalytic species. Fig. 6A shows the TPR-H2 profiles obtained is a consequence of the change in the surface area.
for the Perovskite-Carbon composites and pristine LCMO material The different Perovskite-Carbon composites have been studied
and Fig. 5B shows the TPR-H2 for ball-milled samples prepared at in ORR. Fig. 7A shows the LSV curves obtained in an O2 saturated
different atmospheres and times. Significant differences are solution, and Table 4 summarizes the electrochemical parameters
observed between the LMCO perovskite and the Perovskite- obtained from these curves. Differences between the different elec-
Carbon composites. LMCO shows two regions in the TPR profile; trocatalysts are detected.
the first one between 150 and 600 °C corresponds to the removal Regarding the mixing methods, samples prepared by manual
of adsorbed oxygen (150–250 °C) [40] and the reduction of Mn shaking and using the mortar show lower electrocatalytic activity
(IV) to Mn(III) (250–550 °C) [41]; furthermore, the reduction to than ball-milled samples; that is, less positive onset potential (de-
Co(III) to Co(II) is also produced [42]. The second region between fined as the potential at which the current density reaches 0.1 mA/
600 and 850 °C corresponds to the reduction of Co(II) to Co(0) cm2, as reported elsewhere [45]) and lower limiting current den-
and the main peak at 780 °C is associated with the reduction of sity (Table 4).
Mn(III) to Mn(II) [43]. The results for the Perovskite-Carbon com- In the case of ball-milled samples, it can be observed that
posites (Fig. 6A and 6B) show that the TPR profile for the manually milling time has an important influence on the electrocatalytic
shaken sample is the most similar to the LMCO perovskite, indicat- activity for ORR. In this sense, the sample prepared with a ball-
ing the poor interaction between the carbon material and the per- milling time of 30 min (BM_30_350_O2) reaches a more negative
ovskite. However, the TPR profiles are significantly different for the limiting current density and a higher onset potential than the sam-
sample prepared with the mortar and especially for the samples ples prepared at higher ball-milling times (BM_60_350_O2 and
prepared by ball-milling. The main differences observed for the BM_180_350_O2). Then, the electrocatalytic activity decreases
ball-milled samples are: (i) the reduction processes occur at lower with the ball-milling time, and this trend is also observed for the
temperatures, (ii) the large H2 consumption at 790 °C associated samples prepared by ball-milling in an Ar atmosphere (Table 4).
with the reduction of Mn(III) to Mn(II) disappears and (iii) the Moreover, the rotation speed has no significant effect on the elec-
amount of H2 consumed in the TPR decreases. These results are a trocatalytic activity (Fig. S10A).
consequence of the interaction between both components and Furthermore, it is convenient to analyze the number of elec-
the contribution of the carbothermal reduction, which seems to trons transferred in the reaction to determine whether the reaction
be the main process responsible for the Mn(III) reduction [18]. In occurs through a four-electron path to water (the desirable path),
addition, Fig. S8 shows that the rotation speed does not have a sig- or a two-electron path to hydrogen peroxide (the undesirable
nificant influence. These observations are in complete agreement path). Fig. 7B and Table 4 show the electrons transfer number (n)

Fig. 6. TPR-H2 profiles for different materials: (A) representative examples of different mixing methods and (B) profiles for ball-milled samples at 350 rpm at different
atmospheres and times.

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M. García-Rodríguez, J.X. Flores-Lasluisa, D. Cazorla-Amorós et al. Journal of Colloid and Interface Science 630 (2023) 269–280

Fig. 7. (A) LSV for ORR in 0.1 M KOH saturated with O2 at 1600 rpm. Scan rate: 5 mV/s. (B) Number of electrons transferred in ORR, (C) LSV for OER in 0.1 M KOH saturated
with N2 at 1600 rpm. Scan rate: 5 mV s1. (D) Bifunctional Index.

Table 4
ORR and OER electrochemical parameters obtained in the LSV curves for Perovskite-Carbon composites.

Sample ORR OER BI/

V
Eonset /V (a 0.10 mA/ n (at j/mA cm2 (at Tafel slope/mV/ Potential/V (at 1 mA/ Potential/V (at 4.5 mA/ Tafel slope/mV/
cm2) 0.4 V) 0.4 V) dec cm2) cm2) dec
BM _30_350_O2 0.84 3.6 5.3 76 1.57 1.65 180 0.73
BM_60_350_O2 0.84 3.4 5.0 77 1.61 1.74 259 0.77
BM_180_350_O2 0.82 3.3 4.5 78 1.65 – 239 0.83
BM_30_500_O2 0.83 3.5 5.1 82 1.59 1.71 249 0.76
BM_30_350_Ar 0.84 3.8 5.4 84 1.60 1.68 156 0.77
BM_180_350_Ar 0.82 3.6 4.8 76 1.63 1.75 274 0.81
BM _30_500_Ar 0.81 3.5 4.8 73 1.63 1.73 298 0.82
Mortar 0.82 3.3 4.0 89 1.66 1.76 199 0.83
Manual shaking 0.80 3.3 4.2 118 1.64 – 154 0.84

for the different electrocatalysts. In general, ball-milled samples tains the electrochemical parameters obtained from these LSV. It
show higher electrons transfer number than mortar and manually can be observed that the ball-milled samples have higher electro-
shaken samples. Besides, the ball-milled samples prepared at sim- chemical activity for this reaction than those prepared by other
ilar conditions but in an Ar atmosphere achieve a value of n slightly mixing methods. In particular, the BM_30_350_O2 sample presents
higher than the samples prepared in an oxygen atmosphere (for the highest activity with an Eonset (defined at 1 mA/cm2 [46]) of
instance, see n values of BM_30_350_Ar and BM_30_350_O2 sam- 1.60 V, which is lowest compared to the other samples. A slight
ples in Table 4) being in all cases close to 4. It is worth noting that improvement is observed when the ball-milling is performed in
the highest ball-milling time in both atmospheres produces a the O2 atmosphere with respect to Ar. As in the case of ORR, the
decrease in the number of electrons transferred, which can be a rotation speed has no significant effect (Fig. S10C and Table 4).
consequence of the increase in particle size as detected by XRD In order to study the bifunctionality of the materials, the so-
and the decrease in the extent of perovskite/carbon interphase (i. called bifunctional index (BI) has been calculated. This index is
e, lower number of MAOAC species). the difference between the onset potentials for ORR and OER reac-
Regarding the OER activity, the different electrocatalysts have tions. Fig. 7D plots the onset potentials for ORR and OER for the
been studied by LSV in a N2-saturated atmosphere at 1600 rpm best ball-milled samples and the mortar and manually shaken
reaching a potential where the OER occurs (Fig. 7C). Table 4 con- samples. It can be observed that the BI value is lower for
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M. García-Rodríguez, J.X. Flores-Lasluisa, D. Cazorla-Amorós et al. Journal of Colloid and Interface Science 630 (2023) 269–280

BM_30_350_O2 and BM_30_350_Ar samples, with values of 0.73 air cathode carbon paper loaded with BM_30_350_O2 sample and
and 0.77 V, respectively. Pt/C. Fig. 8B shows the discharge polarization curves of the ZABs.
Finally, Tafel plots for both reactions have been calculated The BM_30_350_O2-based ZAB delivered a peak power density of
(Fig. S11). The Tafel analysis is an effective tool for studying elec- 34.6 mW/cm2 at 67.1 mA/cm2, which are both lower than that of
tron rate-determining processes [47]. In general, low values of Pt/C (69.4 mW/cm2 at 110.1 mA/cm2) due to the superior catalytic
Tafel slopes suggest better ORR and OER activities (considering activity of the commercial catalyst towards ORR. However, when
that the reaction mechanisms are different for both reactions and analyzing the charge and discharge polarization curves (Fig. S12),
that different values will be obtained), because small slopes imply the BM_30_350_O2 electrocatalyst shows better stability. Fig. 8C
faster electron transfer reactions [48,49]. For the ORR analysis, it is presents the galvanostatic discharge curves at 5 and 10 mA/cm2
worth highlighting that the lowest value (i.e., 77 mV/dec) was for BM_30_350_O2 ZAB-containing electrocatalyst, that produces
obtained for the sample BM_30_350_O2 (Table 4). In the case of an energy density of 764 and 738 mAh/g, respectively. These values
the manually shaken sample, the value is very high (118 mV/ are higher than those obtained for the commercial Pt/C catalyst (741
dec), which is a consequence of the high heterogeneity of the sam- and 737 mAh/g, respectively) (Fig. S13). Fig. 8D shows the galvano-
ple as well as the poor Perovskite-Carbon interaction. In the case of static discharge voltages at current densities from 2 to 50 mA/cm2. It
the OER, the BM_30_350_Ar sample has a lower Tafel slope can be observed that the discharge voltages of the BM_30_350_O2-
(156 mV/dec) compared to 180 mV/dec for the BM_30_350_O2 based ZAB are stable, which is essential for practical applications
sample. In conclusion, ball-milled samples prepared with a ball- [50]. The discharge voltage is stable at each current density studied
milling time of 30 min ensure a good perovskite/carbon interaction and remains at  0.85 V even at a high current density of 50 mA/cm2.
(with the formation of MAOAC species) and they have the highest Interestingly, the discharge voltage can be restored to the initial
electrocatalytic activity for ORR/OER. The electrocatalytic activity value after decreasing the current density, revealing the excellent
seems to be somewhat influenced by the atmosphere used; with rate capability of the BM_30_350_O2 electrocatalyst.
the air atmosphere being the one that leads to slightly enhanced Fig. 8E contains the galvanostatic cycling test in which each
activity. Again, the number of MAOAC species formed seems to cycle lasts for 20 min. The BM_30_350_O2-based ZAB exhibits
have an influence on the catalytic activity. long-term durability, and it can operate under stable conditions
Considering the performance of the BM_30_350_O2 sample for for 30 h. In the first cycles, the BM_30_350_O2-based ZAB shows
both ORR and OER, it can be a promising bifunctional positive elec- a charge and discharge voltage of 2.03 and 1.26 V, respectively,
trode in a ZAB. Thus, the following section shows the application of indicating a voltage difference of 0.77 V, thus leading to an initial
this electrocatalyst in a rechargeable ZAB, and the comparison with round-trip efficiency (defined as the ratio of energy consumed to
a commercial Pt/C (20 wt%) electrocatalyst. energy delivered) of 62 %, which is similar to the Pt/C-based ZAB.
The voltage increases with the number of cycles and the efficiency
also decreases for both ZABs. However, at the end of 90 cycles or
4. Rechargeable Zn-air battery after 30 h of continuous charge–discharge cycles, the efficiency
of the BM_30_350_O2 ZAB is reduced to 55 %, while that of the
Rechargeable ZABs were assembled and tested at room temper- commercial Pt/C ZAB is reduced to 52 %. Thus, BM_30_350_O2-
ature, using the device shown in Fig. 8A and Fig. S1, employing as based ZAB have better rechargeability performance than commer-

Fig. 8. (A) Photograph of the ZAB. (B) Discharge polarization curves and corresponding power density plots. (C) Galvanostatic discharge curve at 5 mA/cm2 and 10 mA/cm2.
(D) Discharge curves of the ZAB based on BM_30_350_O2 with current densities from 2 to 50 mA/cm2. (E) Cycling performance of the BM_30_350_O2-based ZAB and its
comparison with commercial Pt/C-based ZAB.

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M. García-Rodríguez, J.X. Flores-Lasluisa, D. Cazorla-Amorós et al. Journal of Colloid and Interface Science 630 (2023) 269–280

cial Pt/C catalysts. Furthermore, because no precious metals are Acknowledgments

used, the cost of the battery using Perovskite-Carbon composite
is significantly lower than that of Pt/C, highlighting its greater eco- The authors would like to thank PID2019-105923RB-I00 project
nomic potential. funded by MCIN/AEI/10.13039/501100011033. J.X. Flores-Lasluisa
thanks the MICINN for the FPI contract (BES-2017-081598). M.
García-Rodríguez thanks for the funding of the Research Initiation
5. Conclusions Scholarship from Vicerrectorado de Investigación y Transferencia
de Conocimiento of the University of Alicante (AII-20-14) and Min-
In this work, electrocatalysts with bifunctional oxygen reduc- isterio de Universidades for the FPU20-01746 grant.
tion reaction and oxygen evolution reaction activity, consisting of
perovskite-type metal oxides and carbon black have been devel- Appendix A. Supplementary material
oped. They are capable of performing as high-efficiency replace-
ment for Pt/C in a Zn-air battery with a similar behavior to Co- Supplementary data to this article can be found online at
doped LaMnO3-Carbon composites found in the literature [51]. https://doi.org/10.1016/j.jcis.2022.10.086.
Firstly, the LaMn0.7Co0.3O3 perovskite was synthesized by a
hydrothermal method and further heat treated and then it was References
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