Chinese Chemical Letters 34 (2023) 107776

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Chinese Chemical Letters

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

High-entropy perovskite oxide BaCo0.2 Fe0.2 Zr0.2 Sn0.2 Pr0.2 O3- δ with triple
conduction for the air electrode of reversible protonic ceramic cells
Jiaxiang Sun, Rongzheng Ren∗ , Hualiang Yue, Wencan Cui, Gaige Wang, Chunming Xu,
Jinshuo Qiao, Wang Sun, Kening Sun, Zhenhua Wang∗
Beijing Key Laboratory for Chemical Power Source and Green Catalysis, School of Chemistry and Chemical Engineering, Beijing Institute of Technology,
Beijing 100081, China

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

Article history: Reversible protonic ceramic cells (RPCCs) show great potential as new-generation energy conversion and
Received 12 July 2022 storage devices. However, the mature development of RPCCs is seriously hindered by the inactivity and
Revised 7 August 2022
poor stability of air electrodes exposed to concentrated vapor under operating conditions. Herein, we
Accepted 22 August 2022
report a high-entropy air electrode with the composition BaCo0.2 Fe0.2 Zr0.2 Sn0.2 Pr0.2 O3- δ (BCFZSP), which
Available online 28 August 2022
shows integrated electronic, protonic and oxygenic conduction in a single perovskite phase and excellent
Keywords: structural stability in concentrated steam. Such triple conduction can spread the electrochemically ac-
High-entropy perovskite oxide tive sites of the air electrode to the overall electrode surface, thus optimizing the kinetics of the oxygen
Triple-conducting oxide reduction and evolution reactions (0.448  cm2 of polarization resistance at 550 °C). As-prepared RPCCs
Air electrode with a BCFZSP air electrode at 600 °C achieved a peak power density of 0.68 W/cm2 in fuel-cell mode and
Reversible protonic ceramic cells a current density of 0.92 A/cm2 under a 1.3 V applied voltage in electrolysis mode. More importantly, the
Hydrogen production
RPCCs demonstrate an encouragingly high stability during 120 h of reversible switching between the fuel-
cell and electrolysis modes. Given their excellent performance, high-entropy perovskites can be promising
electrode materials for RPCCs.
© 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia
Medica, Chinese Academy of Medical Sciences.

In today’s sustainable energy economy, the use of intermittent ter is generated at the cathode, which reduces the dilution of fuel
wind-based and solar electricity generation has exploded, increas- by water.
ing the demand for efficient and reliable energy conversion and Although RPCCs offer distinct advantages, their large-scale com-
storage devices [1]. Reversible protonic ceramic cells (RPCCs) are mercial applications are limited by the unsatisfactory oxygen re-
the most promising developments among long-term and large- duction reaction (ORR) and oxygen evolution reaction (OER) ac-
scale energy conversion and storage [2]. In the application of tivity. These problems arise from lack of a suitable air elec-
RPCCs, the chemical energy from hydrogen is converted into elec- trode. Many RPCCs use mixed ionic and electronic conductor
trical energy when electricity is required and dry pressure hydro- (MIEC) electrodes such as Ba0.5 Sr0.5 Co0.8 Fe0.2 O3− δ (BSCF) and
gen can be electrolyzed for storage from excess solar and wind- La0.6 Sr0.4 Co0.2 Fe0.8 O3− δ (LSCF), which exhibit remarkable electrical
based electricity [3]. Owing to the unique property of proton hop- conductivity and electrocatalytic activity [5]. However, MIECs in
ping between adjacent oxygen atoms, RPCCs exhibit excellent pro- proton-conductive RPCCs are unsuitable for several reasons. First,
ton conductivity, low activation energy (Ea ) at intermediate tem- because MIECs have poor water-absorption capacity, they cannot
peratures (40 0–60 0 °C), and stable performance [4]. In electrolysis provide sufficient protons from the hydration reaction [4]. Second,
mode, dry pressurized hydrogen is continuously generated at the the reactive sites are restricted to a narrow triple-phase bound-
fuel electrode and then stored in an external pressure vessel. This ary (TPB) between the electrode and electrolyte, which suppresses
process lowers the cost by removing the need for a fuel-separation the ORR activity [6]. Third, MIEC electrodes decompose in a high
device. In fuel-cell mode, hydrogen reacts at the anode while wa- vapor-concentration atmosphere thus destabilize the electrochem-
ical performance [7].
To improve the proton conductivity and widen the TPB,
∗
air electrodes that can transport electrons (e− ), oxide ions
Corresponding authors.
E-mail addresses: [email protected] (R. Ren), [email protected] (Z.
(O2− ), and protons (H+ ) are required. Such electrode materi-
Wang). als, called triple-conducting oxides (TCOs), present more reac-

https://doi.org/10.1016/j.cclet.2022.107776
1001-8417/© 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
J. Sun, R. Ren, H. Yue et al. Chinese Chemical Letters 34 (2023) 107776

tive active sites throughout the electrode surface that boost the porting information). Notably, the BCFZSP can maintain pure phase
ORR and OER activities [8]. Some composite electrodes with at a concentrated steam atmosphere with p(H2 O) as high as 50%
triple conductive properties have been reported recently, such atm, suggesting its excellent structure stability (Fig. S2 in Support-
as PrBa0.8 Ca0.2 Co2 O5+ δ –BaCoO3− δ [9], NiO nanoparticle-modified ing information).
Ba0.95 (Co0.4 Fe0.4 Zr0.1 Y0.1 )0.95 Ni0.05 O3− δ [10], and so forth [11]. How- In electrolysis mode, water molecules are adsorbed on the sur-
ever, industrially fabricating composite cathodes are limited by face of oxygen electrode. The adsorption relies on the hydration
a cumbersome process. Thus, more studies have focused on reaction between oxygen vacancies and water molecules, thus gen-
single-phase electrodes [12]. Compared to the composited elec- erating proton defects (Figs. 2a and b). In fuel-cell mode, the water
trode, single TCOs show definite chemical composition, which is formed by the combination of proton defects and lattice oxygen
more suitable for facile preparation and large-scale application. that escapes from the lattice gap (Figs. 2b and c). Therefore, the
A series of classic single TCOs have been developed, including interaction between H2 O and oxygen vacancy contribute greatly to
PrBa0.5 Sr0.5 Co1.5 Fe0.5 O5+ δ [13], BaCo0.4 Fe0.4 Zr0.1 Y0.1 O3− δ (BCFZY) the electrochemical performance of RPCCs. For evaluating this in-
[14], and so forth [15]. In single TCOs, protons are mainly gener- teraction, thermogravimetric analysis (TGA) was carried out (Fig.
ated from the hydration of oxygen vacancies and external water. 2d). First, the samples were heated from the room temperature to
Thus, the design of single TCOs is challenged by the need for plen- 900 °C to form oxygen vacancies. Then the samples were cooled
tiful water uptake at the oxygen vacancies for copious proton pro- under dry and wet air (p(H2 O) = 10% atm) respectively to observe
duction. the adsorption behavior of oxygen and H2 O. A higher weight loss
High-entropy oxides (HEOs) are advantaged by thermal stabil- can be observed for BCFZY during the heating process, meaning
ity and formation of oxygen defects. HEOs are single-phase oxides more vacancies of BCFZY than BCFZSP. Given that the weight loss
containing at least five different cations in equiatomic amounts of perovskite oxides at evaluated temperature is closely related to
[16]. Thus, the multi-functional requirements can be met by select- the reduction of Fe/Co cations, the more vacancies in BCFZY is
ing the appropriate elements. HEOs possess thermodynamic sta- mainly ascribed to more Fe/Co content in BCFZY. During the cool-
bility due to high configuration enthalpy [16]. By virtue of their ing stage, the increase of mass in dry air is attributed to the ab-
outstanding properties, HEOs have been widely applied in energy sorption of oxygen (Eq. 1).
storage and conversion technologies. Liu et al. boosted the Cr-
1
poisoning tolerance of the cathode in solid oxide fuel-cells (SOFCs) V··O + O2 → O×
O + 2h
·
(1)
2
[17]. Liu et al. enhanced and stabilized the ORR performance in
rechargeable metal–air batteries [18]. Wang et al. improved the While cooling in the wet state, both the O2 absorption and H2 O
oxygen evolution activity in effective OER catalysis [19]. However, uptake can lead to the weight increase (Eq. 2).
to the best of our knowledge, HEOs with triple-conductive proper- ·
V··O + H2 O + O×
O → 2OHO (2)
ties have not been reported in RPCCs. Therefore, a suitable design
approach for air electrodes with high electrocatalytic performance Based on the weight difference under different cooling atmo-
and extraordinary stability is vital to RPCCs development. sphere, the proton concentration can be calculated [4]. It is inter-
Herein, BaCo0.2 Fe0.2 Zr0.2 Sn0.2 Pr0.2 O3- δ (BCFZSP), a high-entropy esting that more proton defects can be detected in BCFZSP (Fig.
perovskite oxide, was designed and employed as the electrode for 2e), even though the oxygen vacancy concentration of BCFZSP is
RPCCs. And BCFZY such a classic TCO has been selected as the lower than that of BCFZY. Specifically, the proton concentration
control sample to better analyze the triple conduction of BCFZSP. in BCFZSP at 500 °C and 10% atm p(H2 O) was 6.92 mol%, versus
Compared with the BCFZY, BCFZSP presents a high proton diffu- 1.34 mol% in BCFZY. This result suggests that the water adsorption
sion coefficient. At 600 °C, the BCFZSP electrode with an approxi- capacity of oxygen vacancy in BCFZSP is much stronger than that of
mately 8-μm-thick BaZr0.4 Ce0.4 Y0.1 Yb0.1 O3- δ electrolyte achieved a BCFZY. TG relaxation technique with dry/wet atmosphere switching
peak power density of 677 mW/cm2 in fuel-cell mode. In electrol- was further used to compare the hydration/dehydration capacity of
ysis mode, the current density reached 0.92 A/cm2 at an applied BCFZSP and BCFZY (Fig. 2f). After a rapid change between dry and
voltage of 1.3 V. The eminent polarization resistance was 0.448  wet (p(H2 O) = 10% atm) atmosphere, a sharper weight change sig-
cm2 at 550 °C. More importantly, the full cell degraded minimally nal in BCFZSP reveals a better hydration and dehydration ability
after 120 h operation and completely recovered with no perfor- of BCFZSP. All these results emphasize that the high-entropy per-
mance degradation during 120 h switching cycles. Both the high ovskite oxide shows enhanced hydration/dehydration ability.
ORR activity and excellent stability at low temperatures suggest Electrical conductivity relaxation (ECR) method was further car-
that BCFZSP is a promising high-entropy electrode for RPCCs. ried out to quantify the triple conduction and water exchange
Energy dispersive X-ray spectroscopy (EDS) mapping showed process of the BCFZSP electrode. It should be noted that the
that all the elements are uniformly distributed in BCFZSP sam- ECR used here was performed on a fixed oxygen partial pressure
ple (Fig. 1a), and the estimated atom ratio of Ba:Co:Fe:Zr:Sn:Pr (p(O2 ) = 21%) but a varied p(H2 O). Once the pH2 O is increased, oxy-
matched well with the nominal value for BCFZSP (Table S1 in gen vacancies in perovskite will be occupied, the concentration of
Supporting information). The X-ray diffraction (XRD) Rietveld re- all carriers in TCOs, including the oxygen vacancies, holes (h· ), and
finement results suggest that the BCFZSP showed a single per- proton defects (OH·O ), can be redistributed (Fig. 3), hence forming
ovskite phase with a Pm-3 m space group and a cell parameter of concentration gradient. This mechanism offers a feasible path to
a = b = c = 4.183(5) Å (Fig. 1b and Table S2 in Supporting informa- uncover the triple conduction and water exchange process of the
tion). The estimated lattice fringe distance of 0.295 nm in high- BCFZSP electrode.
resolution transmission electron microscopy (HR-TEM) matched Figs. 4a and b are ECR configurations of BCFZSP and
well with the (101), (011), and (110) facets along the [111] zone BaZr0.4 Ce0.4 Y0.1 Yb0.1 O3- δ (BZCYYb) when switching the atmosphere
axis (Fig. 1c). The corresponding selected area electron diffraction from dry to wet state at 600 °C. A nonmonotonic relaxation curve
(SAED) pattern also confirms this crystal plane alignment (Fig. 1d). can be observed with p(H2 O) suddenly increasing. The conduc-
All of these results indicated the B-site cations were completely tivity of two samples initially dropped and then raised to a new
dissolved into the lattice of HEOs without impure phases. X-ray equilibrium. This nonmonotonic transformation was ascribed to
photoelectron spectroscopy (XPS) results indicate that Co/Fe/Pr ex- hole redistribution during the hydration reaction. Because the elec-
hibite a mixed valence state (Co and Fe: +2/+3; Pr: +3/+4), while tronic conductivity in TCOs is much higher than ionic conductiv-
Zr and Sn cations show fixed valence state of +4 (Fig. S1 in Sup- ity, the conductivity change as function of p(H2 O) is mainly at-

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J. Sun, R. Ren, H. Yue et al. Chinese Chemical Letters 34 (2023) 107776

Fig. 1. Crystal structure of the high-entropy BCFZSP perovskite: (a) EDS maps of Ba, Co, Fe, Zr, Sn, Pr, and O. (b) Rietveld refinement room-temperature XRD pattern; (c)
HR-TEM image; (d) SAED pattern along the [111] zone axis.

Fig. 2. Schematics of (a) H2 O adsorption from air to oxygen vacancies, (b) formation of proton defects, and (c) H2 O desorption from oxygen vacancies to air. (d) Cooling TG
plots in dry and wet atmospheres. (e) Calculated proton concentrations in the BCFZSP and BCFZY samples. (f) Thermogravimetric relaxation curves based on rapid switching
from dry to wet (p(H2 O) = 10% atm) condition.

·
holes (2H + 2h −→ 2H+ , Fig. 3b). Thus, the diffusion of O2− in-
creases hole concentration, while the transfer of H+ decreases the
hole concentration. Those two concurrent opposite influence on
hole concentration results in nonmonotonic conductivity change.
The initial drop of conductivity reveals the quicker diffusion of
H+ than that of O2− in BCFZSP. As a contrast, the conductivity
of BCFZY increases first and then decreases (Fig. 4c), suggesting a
slower diffusion of H+ than the O2− in BCFZY. These results qual-
itatively demonstrate that BCFZSP manifests much more excellent
proton mobility than the classic BCFZY material, showing great ap-
plication potential in RPCC in light of the important effect of pro-
ton transfer on the electrode performance.
The comparison of Figs. 4a and c indicates that the elec-
Fig. 3. Schematics of hole redistribution and proton migration as p(H2 O) increases:
(a) combination of water and oxygen vancy, (b) hole redistribution, (c) proton trans- tronic conductivity of BCFZSP is lower than that of BCFZY. Given
fer. that the electronic conduction is formed by hole jumping be-
tween the Co(Fe)–O–Co(Fe) bonds, the lower electronic conductiv-
ity of BCFZSP can be explained by its less Co/Fe composition ra-
tio. Furthermore, parameters for quantifying ion conduction, in-
tribute to hole concentration. During hydration, O from H2 O gen-
· cluding chemical diffusion coefficients of oxygen ions (DO,chem )
erates holes (O + V··O −→ O×O
+ 2h ) while H from H2 O consumes

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J. Sun, R. Ren, H. Yue et al. Chinese Chemical Letters 34 (2023) 107776

Fig. 4. ECR curves of (a) BCFZSP, (b) BZCYYb, and (c) BCFZY under p(H2 O) switching from dry to 10% atm at 600 °C; Fitted (d) DO,chem , (e) DH,chem , and (f) kwater plots of the
BCFZSP, BCFZY, and BZCYYb samples.

and protons (DH,chem ) and exchange coefficient of water (kwater ),

were calculated by fitting the ECR data with diffusion equations
(Eqs. S4–S7) in Supporting information). Figs. 4d–f show the Ar-
rhenius curves of DO,chem , DH,chem and kwater , respectively. The Ea
of DO,chem in BCFZSP was lower than that of BCFZY, revealing a
lower energy barrier for oxygen-ion migration in BCFZSP. BCFZSP
also presents excellent proton mobility and water exchange coef-
ficient. For instance, from 500 °C to 700 °C, the DH,chem (3.05–
22.37 × 10−6 cm2 /s) and kwater (2.01–21.29 × 10−5 cm/s) of BCFZSP
are much higher than those of BCFZY (DH,chem : 6.69–42.50 ×
10−7 cm2 /s, kwater : 7.49–106.30 × 10−6 cm/s) and BZCYYb (DH,chem :
1.31–11.36 × 10−6 cm2 /s, kwater : 4.89–58.61 × 10−6 cm/s).
The electrochemical impedance spectroscopy results display
that BCFZSP shows the polarization resistance (Rp ) of 0.448  cm2
(Fig. S3 in Supporting information), about half of that of BCFZY
(0.932  cm2 ). It is also noted that the Rp and Ea values of BCFZSP
decrease with increasing p(H2 O), indicating the positive effect of
proton transfer on extending the active sites of ORR and OER [20].
The performance of BCFZSP under actual cell operating conditions
was evaluated in an anode-supported single cell composed of the
NiO-BZCYYb anode, BZCYYb electrolyte (∼8 μm) and BCFZSP elec-
trode (Fig. 5a). In fuel-cell mode, the single cell displayed high
peak power densities of 0.93, 0.79, 0.67, 0.48 and 0.33 W/cm2 at
Fig. 5. (a) SEM image of an RPCC with the Ni-BZCYYb anode, BZCYYb electrolyte,
700 °C, 650 °C, 600 °C, 550 °C and 500 °C, respectively (Fig. 5b).
and BCFZSP electrode. (b) Output performance in fuel-cell mode. (c) I–V curves
These results are superior to BCFZY (Fig. S4 in Supporting infor- measured in electrolysis mode. (d) Hydrogen production rates, (e) Faradaic efficien-
mation). Fig. 5c presents the current–voltage (I–V) curves in elec- cies, and (f) energy efficiencies of current density in electrolysis mode.
trolysis mode at 50 0–70 0 °C with pH2 O = 20%. At an applied volt-
age of 1.3 V, the current density reached 0.35, 0.61, 0.92, 1.20, and
1.76 A/cm2 at 500 °C, 550 °C, 600 °C, 650 °C, and 700 °C, respec-
tively. BCFZSP surpasses BCFZY in current density at each temper-
ature (Fig. S5 in Supporting information) and dominates over most
of those previously reported air electrodes (Table S3 in Support-
ing information). It can be also noted that hydrogen production
rate in same current density decreased as temperature increased
(Fig. 5d), indicating the lower Faraday efficiency of electrolysis at
the high temperature (Fig. 5e). This result can be attribute to in-
creased electron leakage on protonic electrolyte as temperature in- Fig. 6. (a) Stability tests in fuel-cell and electrolysis modes; (b) stability test during
creased [21]. The energy efficiency at 600 °C in electrolysis mode several cycles of switching between fuel-cell and electrolysis modes.
(Fig. 5f) reached 68.76%, 63.68%, 62.14%, 58.65%, 55.32% and 53.34%
at −0.75, −1, −1.25, −1.5, −1.75 and −2 A/cm2 , respectively.
Long-term stability was confirmed under a constant current served throughout 5 reversible switching cycles (120 h). The excel-
density of −1.3 A/cm2 in electrolysis mode and 0.61 A/cm2 in fuel- lent electrochemical stability suggests that high-entropy BCFZSP is
cell mode at 600 °C (Fig. 6a). Furthermore, stability cycling when a promising air electrode for RPCCs.
switching between the fuel-cell and electrolysis modes was tested In summary, RPCCs electrode BCFZSP with cubic structure was
at 600 °C (Fig. 6b). Inappreciable performance degradation was ob- successfully fabricated by a high-entropy design strategy, which

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J. Sun, R. Ren, H. Yue et al. Chinese Chemical Letters 34 (2023) 107776

had high electrochemical performance and stability. Compared Supplementary materials

with BCFZY, BCFZSP presented a higher proton diffusion coefficient.
The BCFZSP electrode was successfully applied in RPCC. At 600 °C, Supplementary material associated with this article can be
the peak power density reached 0.68 W/cm2 in fuel-cell mode. found, in the online version, at doi:10.1016/j.cclet.2022.107776.
The current density reached −0.92 A/cm2 at 1.3 V in electrolysis
mode. More importantly, the stability remained 120 h of reversible References
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