Applied Energy 336 (2023) 120788

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Layer-structured Li1-xNaxNi0.8Co0.15Al0.05O2-δ oxide anode for enhancing

ceria electrolyte based solid ceramic fuel cell operating at lower
temperatures down to 370 ◦ C
Liwen Huang a, Jia Wang b, Wen-Feng Lin c, Yan Wu a, *
a
Engineering Research Center of Nano-Geo Materials of Ministry of Education, Faculty of Materials Science and Chemistry, China University of Geosciences, 388 Lumo
Road, Wuhan 430074, China
b
Shaanxi Key Laboratory of Nanomaterials and Nanotechnology, School of Mechanical and Electrical Engineering, Xi’an University of Architecture and Technology,
Xi’an 710055, Shaanxi, China
c
Department of Chemical Engineering, Loughborough University, Loughborough, Leicestershire LE11 3TU, United Kingdom

H I G H L I G H T S

• Layered LNNCA anode enabled fuel cell operating temperatures down to 370 ◦ C.
• Doped Na+ decreased Li+/Ni2+ intermixing to maintain skeleton stability of LNNCA.
• Na-doping introduced affluent oxygen vacancies to provide reactive active sites.
• The dissociation of adsorbed hydrogen on LNNCA improve HOR activity.

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

Keywords: A ceria electrolyte-based solid ceramic fuel cell (SCFC) with a layer-structured Li1-xNaxNi0.8Co0.15Al0.05O2
Layer-structured oxide anode (LNNCA) anode has been developed. The fuel cell with LNNCA anode achieved a maximum power density of 884
Sodium doping mW cm− 2 at 550 ◦ C, which is about 1.6 times higher than the pristine LNCA anode. Meanwhile, the L0.8N0.2NCA
Hydrogen oxidation reaction
anode presents a good low temperature characteristic, and it could still be operable at 370 ◦ C with the power
Low temperature solid ceramic fuel cell
density of 63 mW cm− 2. The anchoring effect of doped Na+ plays a vital role in maintaining the layered structure
of LNNCA. It decreases Li+/Ni2+ intermixing, and inhibits Ni growing on the surface of LNNCA, which enhance
the catalytic activity and electrical contact of the anode with the ceria electrolyte. Furthermore, Na-doping
enriches oxygen vacancies, and promotes the dissociation of adsorbed hydrogen on the surface of LNNCA
anode, and thus improves the hydrogen oxidation reaction activity. On the other hand, the in-situ grown NaOH,
which has a low-melting temperature, derived from LNNCA anode, can effectively strengthen the bonding be­
tween the anode and the electrolyte at the interface, as well as penetrate into electrolyte and provide extra
transport channels for proton and other ions, thus decrease the polarization resistance and enable the SCFC to
performance even at 370 ◦ C.

1. Introduction convert chemical energy of hydrogen fuel to electricity directly via

electrochemical reactions on anode and cathode electrodes with only
Solid ceramic fuel cells (SCFCs) have been developed as an envi­ pure water as the by-product to generate the clean electricity [2].
ronmentally friendly energy conversion technology, which possesses a Nevertheless, SCFCs still face significant challenges in achieving wide
high efficiency beyond the restriction by Carnot cycle [1]. The fuel cells commercialization due to the durability concerns at material and system

Abbreviations: PCFCs, Proton-conducting ceramic fuel cells; SCFCs, Solid ceramic fuel cells; LNCA, LiNi0.8Co0.15Al0.05O2-δ; LNNCA, Li1-xNaxNi0.8Co0.15Al0.05O2-δ;
L0.8N0.2NCA, Li0.8Na0.2Ni0.8Co0.15Al0.05O2-δ; EIS, Electrochemical impedance spectroscopy; OCV, Open circuit voltage; TPB, Three-phase boundaries; HOR, Hydrogen
oxidation reaction; ORR, Oxygen reduction reaction; Rp, Polarization resistance.
* Corresponding author.
E-mail address: [email protected] (Y. Wu).

https://doi.org/10.1016/j.apenergy.2023.120788
Received 27 October 2022; Received in revised form 28 December 2022; Accepted 3 February 2023
Available online 15 February 2023
0306-2619/© 2023 Elsevier Ltd. All rights reserved.
L. Huang et al. Applied Energy 336 (2023) 120788

levels, at the high temperature (800–1000 ◦ C) operation [3]. factors comprehensively, doping with suitable ions instead of using
The SCFC consists of three parts: anode, electrolyte, and cathode. coating is a much better way to solve these issues [30,31]. By limiting
Anode plays important role in SCFC, catalyzing the oxidation reaction of nickel ion migration into the lithium ion layer, potentially appropriate
the fuel and conducting the produced electrons to the external circuit ions could be used to dope the LNCA to improve the stability of its
[4,5]. Proton exhibits lower migration energy than oxygen ion, therefore layered structure [32]. In addition, Chen et al. reported that the LiOH/
one of the most feasible ways to develop lower temperature SCFCs is to Li2CO3 formed in LNCA anode diffused into electrolyte and provided
explore the proton conducting ceramic electrolyte fuel cell [6–8]. In affluent oxygen vacancies for ionic conduction [24]. This was regarded
proton conducting SCFC, the proton is produced at anode, which is then as the key to maintain a high performance for LNCA electrode at a lower
transported through proton conducting electrolyte and reacts with ox­ temperature.
ygen molecules at the cathode. Hence, exploring potential anode ma­ Doping appropriate elements into oxides could improve physical-
terials with high HOR activity are of great significance for the chemical properties of materials including stability and ion/electron
development of low temperature proton conducting fuel cells. Several conduction [33]. Na ion can be used as an ideal doping agent for lithium
parameters are considered when selecting candidate anode materials, cation substitution, as sodium ion is low-cost, abundant in the earth, and
including adequate electrical conductivity, ionic conductivity, catalytic possessing with a proper ionic radius. On the one hand, Na and Li be­
activity, thermal expansion compatibility and porosity [9,10]. So far, longs to alkali-metals, they exhibit similar chemical characteristics,
the available anode materials are porous metal and cermet electrodes. which could better maintain the stability of the layered structure. On the
Porous metal electrodes (Ag, Pt, Ni, Fe, and Mn) exhibit good electronic other hand, the reported LiOH/Li2CO3 formed in LNCA anode could
conductivity in high temperature and reductive environment [11]. diffuse into the electrolyte and hence optimize the contacting interface
Noble metal Pt has been used in electrodes with a good catalytic activity [34]. While the cell containing Li element compounds only could
[12], but the adhesion between Pt and the solid oxide electrolyte operate above 430 ◦ C [22]. Compared to Li compounds (LiOH/Li2CO3),
decreased after long-time operation. Porous Ni is also considered as a the introduced Na-element compounds (NaOH/Na2CO3) with a lower
low-cost potential anode with good catalytic activity [13], while the melting temperature (above 318 ◦ C) could contribute to the lower
drawback of its low sintering temperature (1000 ◦ C) restricts the oper­ temperature operation of the fuel cell [35].
ation conditions. The cermet-based materials are also widely used as In the above context, the sodium cation doping strategy was applied
anode materials including doped ceria, barium zirconate and barium to tailor the layer structured LiNi0.8Co0.15Al0.05O2-δ (LNCA) for the SCFC
cerate [14,15]. However, the exists SCFC technology still faces the anode, by a facile sol-gel method in this study. The optimum Na dopant
challenge of lowering the operating temperature for achieving lower ratio to the Li was investigated, in terms of the electrochemical prop­
operating costs and broad selecting ranges of materials [16]. erties, as well as the PCFC performances. The synthesized Na-doped
Recently, nickel-rich layered oxides have been identified as prom­ LNCA, Li1-xNaxNi0.8Co0.15Al0.05O2-δ to be named as LNNCA, exhibited
ising anode electrode materials for lower temperatures SCFC [17,18]. an impressive HOR catalytic activity, with the PCFC employing the
Fan et al. [19] developed the layer-structured LiNi0.8Co0.2O2 for lower LNNCA anode showed a high peak power density of 884 mW cm− 2 at
temperature proton conduction in SOFC, and the maximum power 550 ◦ C, whilst still being operable at 400 ◦ C with power density
density reached 410 mW cm− 2 at 550 ◦ C. LiNi0.8Co0.15Al0.05O2-δ (LNCA) remained up to 118 mW cm− 2 and a polar resistance of 5.33 Ω cm2. As
related to LiNiO2, where a fraction of the nickel cations has been far as we known, this is the first work about LNCA electrode doping
replaced by cobalt and aluminum cations, which has been widely used in modification with alternative elements in SCFC field. The layer struc­
the field of solid-state batteries [20]. While aluminum ions, which are tured LNNCA and the Na doping strategy could be adopted to fabricate
redox inactive, enhance the thermal stability of the layered oxides, co­ enabling electrodes for advanced lower temperature solid oxide fuel
balt ions stabilize the alternating layered structure [21]. The LNCA has cells, particularly the recently reported promising proton-conducting
been proved as a triple (H+/O2− /e− ) conducting electrode material that ceramic fuel cells (PCFCs).
has great application prospects in the field of low temperature solid
oxide fuel cells [16]. Chen et al. [22] discussed influence of layered 2. Experimental
LNCA electrode on promoting the low temperature operation for SCFC.
The cation-disordered “NiO-like” phase and Li2CO3 composite in the 2.1. Preparation of materials
melted and partial melted states in the high temperature region was
mentioned to contribute high ionic conductivity and lower activation All the chemical agents were purchased from Sinopharm chemical
energy for oxygen reduction reactions (ORR). Dong et al. investigated reagent co. LTD, including Al(NO3)3⋅9H2O, LiNO3, NaNO3, Ni
the layer-structured LixNi0.8Co0.15Al0.05O2-δ (x = 1, 1.2, 1.4) with (NO3)2⋅6H2O, Co(NO3)2⋅6H2O and citric acid with purity of 99.5%.
different lithium content, and the Li+ is proved to play vital role for L1-xNxNCA (x = 0, 0.1, 0.2, 0.3, 0.4) was synthesized by sol-gel hydro­
hydrogen oxidation reaction and oxygen reduction reaction [23]. thermal method, 0.1 mol LiNO3, 0.08 mol Ni(NO3)2⋅6H2O, 0.015 mol Co
Although LNCA electrodes have been widely recognized, the stability (NO3)2⋅6H2O and 0.005 mol Al(NO3)3⋅9H2O were dissolved in 150 mL
concern still needs to be addressed for wider commercial applications in distilled water with vigorous stirring, NaNO3 was used to replace the
the SCFC field [24]. For example, layer structured LNCA anode could be LiNO3 in a certain proportion; subsequently, citric acid solution was
transformed into a Ni rich surface after a prolonged exposure to gradually added to form sol gradually; the mixed solution was contin­
reductive atmosphere feeding with hydrogen fuel. The internal strain uously stirred in an oil bath at 110 ◦ C for 8 h, and then transferred to an
generated by the phase transition could cause the layered structure to oven for 12 h, the products so obtained were served as precursors, which
collapse and, as a result, the electrode electrical contact would be lost. were calcined in a muffle furnace at 520 ◦ C for 4 h, and finally sintered at
Furthermore, LNCA is moisture-sensitive, which can lead to decrease in 900 ◦ C for 4 h.
electrochemical performance [25]. The coating approach is one of
feasible strategies to improve the layered-oxide electrode materials in 2.2. Electrode and fuel cell fabrication
general [26,27]. The ionic conductor Li2ZrO3 with an ionic conductivity
around 10− 5–10− 4 S cm− 1 at 300–600 ◦ C was used as a coating layer to Ethanol and terpineol mixed solution (volume ratio 1:1) was added
enhance catalytic activity and stability of LNCA electrode in our previ­ into LNNCA powder to form homogeneous slurry. The mass ratio of
ous work [28]. However, the addition of the coating layer inevitably LNNCA solid powder to the mixed solution is 5:2. The load of LNNCA on
affected the electrochemical activity and microstructures, such as grain the Ni foam is about 1.5–2 g (The area is about 0.64 cm2). The prepared
size, composition, phase distribution and three-phase boundaries (TPB) slurry was brushed on the electrode substrate Ni-foam, and dried in oven
of the electrode-electrolyte interfaces [29]. After considering these at 100 ◦ C for 2 h to obtain Ni-LNNCA electrode as anode. The LNCA-Ni

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L. Huang et al. Applied Energy 336 (2023) 120788

Fig. 1. (a) Schematics showing the structure changes from LNCA to LNNCA after Na doping, (b) XRD patterns of the as-synthesized Li1-xNaxNi0.8Co0.15Al0.05O2-δ (x =
0, 0.1, 0.2, 0.3, 0.4), (c) the enlarged pattern of (0 0 3) plans, the XPS spectra of O 1s (d) and Ni 2p (e) from LNCA and L0.8N0.2NCA.

electrode was prepared in the same way and was used as cathode. The 2.3. Characterizations
0.30 g commercial CeO2 power (Beijing Zhongkeleiming Daojin Tech­
nology Co., LTD, 99.99%) was employed as the electrolyte material The crystal structure of samples was characterized by using an X-ray
which was sandwiched between the two electrodes and then pressed diffractometer (XRD, D8-Focus, Bruker, Germany) with Cu Kα radiation
with a pressure of 350 MPa for 2 min, the obtained Ni-LNNCA/CeO2/ (λ = 1.54060 nm). The surface morphologic characteristics and
LNCA-Ni membrane-electrode-assembly (MEA) was used for the fuel cell composition were investigated on scanning electron microscope (SEM,
tests. The active area and thickness of the MEA were 0.64 cm2 and 0.55 TESCAN MIRE LMS, Czechia). The powder samples were dispersed on
mm, respectively. specimen holder using ethanol as dispersing media and conductive tape,
and Pt was sprayed on all testing samples before SEM test. The detailed
morphology and crystal structure (interplanar distances) of materials
were characterized by a high-resolution transmission electron

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L. Huang et al. Applied Energy 336 (2023) 120788

Fig. 2. (a) SEM image of synthesized LNCA, and (b) Ni, Co, Al, O elements mappings of square area, (c) SEM image of synthesized L0.8N0.2NCA, and (d) Ni, Co, Al, Na
elements mappings of square area.

microscope (TEM, JEOL, JEM-2100F, Japan). The electron structure of M− O (M = Ni, Co, Al) octahedron. Due to the existence of Ni2+ and Li+
samples was characterized by an X-ray photoelectron spectroscopy with similar radii, it is easy to cause Li+/Ni2+ mixing, resulting in
(XPS, K-Alpha 250XI, Thermo Scientific, USA). The LNNCA and CeO2 structural stability reduced. Herein, we designed to replace part of Li by
samples after test were collected by cutting the anode layer of the tested doping Na with similar chemical properties, and the pinning effect
fuel cell from the electrolyte layer using a doctor blade. might be helpful to improve the structural stability. Fig. 1(b) presents
The performance of fuel cell device was investigated by a fuel cell the XRD patterns of the as–synthesized Li1-xNaxNi0.8Co0.15Al0.05O2-δ,
testing setup (ITECH-8511 electronic load, China) at various operating named as L1-xNxNCA, with x = 0, 0.1, 0.2, 0.3, 0.4. The main diffraction
temperatures with the current scanning range of 0–2 A. Using the ob­ peaks corresponded to hexagonal LiNiO2 layered structure [32]. The
tained voltage power density and current density values, the I-V (cur­ diffraction peaks at 2θ = 18.7◦ , 36.8◦ , 38.5◦ , 44.6◦ , 48.7◦ , 58.8◦ , 64.5◦ ,
rent–voltage) and I-P (current-power) characteristics curves were and 68.5◦ are corresponding to characteristic lattice plane of (0 0 3),
plotted. The hydrogen gas (99%) with a flow rate of 100 mL min− 1 and (1 0 1), (0 1 2), (1 0 4), (0 1 5), (1 0 7), (0 1 8) and (1 1 3) respectively in
the air with a flow rate of 150 mL min− 1 were supplied to the fuel cell undoped samples, indexed to layered LNCA (PDF:98-009-8451) without
anode and cathode, respectively. any impurity phase. All the diffraction peaks of the Na-doped samples
The electrochemical impedance spectroscopy (EIS) was measured by are consistent to that of pristine LNCA, with no impurity phase observed.
an electrochemical workstation (Zahner, Zennium-E, Germany). The For Na-doped LNNCA, a noticeable shift of the pattern of (0 0 3) plan to
scan frequency was in the range of 0.1 M Hz–0.1 Hz. The AC amplitude the low angle direction was observed (Fig. 1(c)), which is due to the
was 10 mV. The obtained EIS data was fitted with an equivalent circuit larger radius of Na+(102 pm) compared with Li+ of 76 pm, indicating
model using ZSIMPWIN software. lattice volume expansion. Furthermore, the ratio of I (0 0 3)/I (1 0 4)
related to the degree of doping ratio of Li+/Ni2+ [21]. It can be seen that
3. Results and discussion the I (0 0 3)/I (1 0 4) value of LNNCA (x = 0.2, 0.3) approaches 1.2,
relating to the low degree of Li+/Ni2+ mixing with layered structure
3.1. Structure and morphology [36]. When the doping ratio reached x = 0.4, the I (0 0 3)/I (1 0 4) value
reached almost 1, indicating that the excessive Na doping increased the
Fig. 1(a) illustrates the evolution of LNNCA layered structure during mixing degree of Li+/Ni2+ and significantly reduced the order of the
Na doping process. The crystal structure of LNCA is a typical layered layered structure [20,37].
structure (space group R3m), with Li intercalation between layers of Fig. 1(d) shows the XPS spectra of O 1s from LNCA and L0.8N0.2NCA.

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L. Huang et al. Applied Energy 336 (2023) 120788

Fig. 3. (a) TEM and (b) HRTEM images, (c) high-angle annular dark field (HAADF) image and (d) Ni, (e) Co, (f) Al, (g) Na, (h) O elements mappings of the syn­
thesized L0.8N0.2NCA.

Three peaks observed with binding energies of 529.13 eV, 531.10 eV, [38,39]. In L0.8N0.2NCA, the banding energy of 2p1/2 and 2p3/2 signals
and 532.19 eV, are assigned to LNCA lattice oxygen (OL), oxygen va­ was centered at 855.18 eV and 872.68 eV, respectively. In comparison to
cancy (Ov) and adsorbed oxygen (Oa) respectively [22]. The contents of LNCA, there is a modest shift in the Ni 2p3/2 signal towards lower
lattice oxygen and oxygen vacancy are 42.7% and 36.4%. Compared to banding energy. Abundant oxygen vacancies were formed on the surface
LNCA, the O 1s spectrum from L0.8N0.2NCA consists of four peaks of LNNCA owing to Na doping, Ni ions maintain a low valence state or
centered at binding energies of 529.06 eV, 531.07 eV, 532.31 eV, move towards a low binding energy to hold the balance of charge, which
534.75 eV, they are assigned to OL, Ov, Oa and adsorbed H2O (OH2O) corresponds to the shift of Oa peak in the direction of high binding
respectively [36]. The contents of lattice oxygen and oxygen vacancy are energy.
24.3% and 62.5%. Compared to LNCA, the content of oxygen vacancy in The morphology of the synthesized samples was investigated by SEM
L0.8N0.2NCA increased significantly, attributing to Na doping leading to as shown in Fig. 2. It can be seen from Fig. 2(a) that the LNCA particles
lattice expansion and thus resulting in more oxygen vacancies. In are made up of large numbers of nanoparticles with irregular poly­
addition, the binding energy of Oa in the LNNCA increased slightly, hedron, the particle sizes are in the range of 200–600 nm. The element
indicating that the electron density decreased. The spectra of Ni 2p are distribution of the prepared LNCA powder was characterized by the
depicted in Fig. 1(e). The Ni 2p spectrum of LNCA centered at banding energy-dispersive X-ray spectroscopy (EDS), with 4 elements of Ni, Co,
energy of 855.30 eV and 872.73 eV, assigned to 2p1/2 and 2p3/2 signals Al, O shown in Fig. 2(b). The Na doped LNNCA samples remain irregular

5
L. Huang et al. Applied Energy 336 (2023) 120788

Fig. 4. (a) I-V and I-P characteristics of the fuel cells operated at 550 ◦ C with various L1-xNxNCA anodes; (b) I-V and I-P characteristics of the fuel cell with
L0.8N0.2NCA anode operated at different temperatures; the Nyquist curves of the fuel cell with LNCA (c) and L0.8N0.2NCA (d) anodes operated at different tem­
peratures; the corresponding distribution of relaxation time plots of LNCA (e) and L0.8N0.2NCA (f) anodes; all the fuel cells were operated with H2 and air feeding into
anode and cathode, respectively.

polyhedron structures and uniform distribution, indicating that the Na current density data obtained from the fuel cells operated at 550 ◦ C with
doping has not impacted on the crystallization, as shown in Fig. 2(c). the various L1-xNxNCA anodes in the MEA configuration of
The EDS mapping of L0.8N0.2NCA is shown in Fig. 2 (d), the distributions Ni–L1-xNxNCA/CeO2/LNCA–Ni, and with H2 and air feeding into anode
of Ni, Co, Al and Na were mapped out. and cathode, respectively. It has been shown that with the Na doping
Fig. 3(a) shows the TEM image of the synthesized LNNCA samples. ratio increased to 20%, the maximum power density of the fuel cell
The interplanar spacing is 0.48 nm, which is consistent with the (0 0 3) reached 884 mW cm− 2, which is 1.6 times higher than that obtained
plans as shown in Fig. 3(b). In the case of sodium ion with a large radius, from the pristine LNCA anode. Nevertheless, the excessive Na doping
the diffraction peak of (0 0 3) plane show a noticeable shift toward lower beyond 20% led to the decrease in the power density owing to the
angle verified by XRD results, and the measured value of (0 0 3) inter­ increased mixing degree of Li+/Ni2+ and the reduced order of the
planar spacing is slightly larger than the theoretical value (0.472 nm) in layered structure, especially for the 40% Na-doping (i.e., L0.6N0.4NCA)
LNCA[21], indicating that the doped Na caused the expansion of c-axis testified by XRD results. Fig. 4 (b) displays the I-V and I-P characteristics
directly without structural change[40]. The HADDF and elements of the fuel cell with the optimum L0.8N0.2NCA anode at various tem­
mapping analysis revealed further details of the synthesized Na doped peratures. A high open circuit voltage (OCV) of 1.10 V was obtained,
LNNCA. Obviously, Ni, Co, Al and Na elements distribute homogenously which is close to the thermodynamic (Nernst) theoretical potential at
without any accumulations or segregation, indicating that Na is incor­ that temperature (550 ◦ C that is 823 K) [41]. The power output
porated into the LNCA lattice homogeneously. decreased at the lower operation temperatures, with a power density
remained up to 516, 344 and 63 mW cm− 2 at 460, 430 and 370 ◦ C,
respectively; this is still a significant performance at the relatively low
3.2. Electrochemical properties temperature [42]. The lower temperature operation had an impact on
both electrode kinetic and electrolyte conductivity, the latter decreased
Fig. 4 (a) shows the voltage and power density as a function of

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L. Huang et al. Applied Energy 336 (2023) 120788

Fig. 5. (a) The Ro, Rp and (b) Arrhenius plots of the log of the Rp resistances for L1-xNxNCA and LNCA anodes in the SOFCs, (c) Nyquist curves obtained from the two
fuel cell configurations of using LNCA as both anode and cathode, and L0.8N0.2NCA as both anode and cathode, operated with H2 feeding at both anode and cathode
sides at 550 ◦ C.

sharply with the decrease of temperature below 460 ◦ C (see the I-V data gas diffusion. The resistance of low-frequency stage peak P4 exhibits an
in Fig. 4b). It was note that for the fuel cell with pristine LNCA anode, inverse temperature dependence, and the resistance of this stage
the power density only remained up to 78 mW cm− 2 at 430 ◦ C, but it still increased with decreasing temperature. Meanwhile, the electrode elec­
remained about 300 mW cm− 2 from the fuel cell with the optimum trochemical process arc is separated into two peaks P2 (1.5 × 10− 3 s) and
L0.8N0.2NCA anode. The corresponding EIS data of LNCA and P3 (1.2 × 10− 2 s) at 460 ◦ C, indicating the significant change of elec­
L0.8N0.2NCA anodes is shown in Fig. 4(c) and (d). It is noted that the trochemical reaction and charge transfer at the TPB on the electrode. In
semicircle diameters increase dramatically with the temperatures addition, P3 peak representing the electrochemical reaction increased
reducing, indicating that the kinetics of electrodes obviously affected sharply, indicating that the chemical reaction process was seriously
with the operation temperatures. Therefore, the electrochemical char­ hindered at 370 ◦ C. According to the report by Osinkin [48], the low rate
acteristics of the two cells under the performance mutation temperature of dissociation of adsorbed hydrogen on the electrode surface de­
(550, 460 and 370 ◦ C) should be further compared in detail. termines the rate of hydrogen oxidation. Herein, a slight shift in the DRT
The distribution of relaxation times (DRT) has been recommended as peaks to higher frequencies especially for P4 can be detected in the fuel
a method to separate highly overlapping physico-chemical processes cell with L0.8N0.2NCA anode compared with that using LNCA anode in
within similar frequency band. It has many successful cases in the field Fig. 4(f), which can be assumed that the dissociation of adsorbed
of electrochemical evolution of the fuel cells [43]. This analysis method hydrogen on the surface of anode might be effectively optimized. In
improves the resolution of EIS data by transforming it from the fre­ addition, the electrode electrochemical process arc of P3 remained in a
quency to the time domain via the following Eq. (1) [44,45]: relatively stable state, and the P2 can be detected slightly at 370 ◦ C.
∫∞ Combined with the I-V and I-P data of the fuel cell, the detected tem­
γ(ln τ)
Z(ω) = jωL0 + R0 + dlnτ (1) perature of split peak P2 in the fuel cell with L0.8N0.2NCA anode is lower,
− ∞ 1 + jωτ
indicating that the surge of electrode polarization caused by the loss of
interface contact was delayed to 370 ◦ C, which might be the crucial
where L0 is an inductance, R0 is ohmic resistance, j is the complex unit,
the characteristic time constant τ is the inverse of angular frequency: reason for the promotion of low temperature performance.
1 In order to investigate the effect of electrochemical reaction on
τ = (2πf)− = ω− 1 . ϒ(ln τ) is the distribution function of relaxation
L0.8N0.2NCA anode upon the bulk resistance, the Ro at different tem­
times for the electrochemical system studied on the logarithmic. The
peratures were compared in Fig. 5(a). Ro of the fuel cell with
establishment of the DRT equation requires ensuring that Z(ω) con­
L0.8N0.2NCA anode is approximate to that with LNCA anode owing to the
verges at the limit ω → 0. It should be noted that the research object in
similar composition at temperatures above 490 ◦ C, which hold the
this work meets this condition, and the non-convergence of the spectrum
similar ionic conduction. However, it exhibits a steep rise at 460 ◦ C in
at the low-frequency cut-off frequency (0.1 Hz) of EIS is due to limited
the fuel cell with LNCA anode. The increase of the charge transfer
working conditions. The distribution relaxation time reflects the time
resistance will influence the ionic conductivity directly, which is one of
required for the fuel cell system to transit from one equilibrium to
significant factors caused the sudden decrease of the power output. Chen
another under small disturbance, and the different chemical processes
et al. [24] proposed that the LiOH/Li2CO3 formed on LNCA anode dif­
correspond to different relaxation time [46]. The obtained impedance
fuses into the electrolyte, which is the significant cause of ionic con­
plots comprise the electrode and grain-boundary arcs [47]. All DRT
ductivity decreased below 425 ◦ C. In contrast, the Ro in the fuel cell with
results in this work were completed by using DRTtools provided by
L0.8N0.2NCA anode was optimized below 460 ◦ C. The optimization may
Francesco Ciucci group [44].
be due to the formation of Na2CO3/NaOH originated from Na modified
Comparing the DRT results of the two fuel cells with different anodes
anode, and the low molten point of NaOH can further optimize the ion
in Fig. 4(e) and (f), several similar features can be observed that suggest
transport at the interface of anode/electrolyte, realizing the low-
the power output of the fuel cell is mainly limited by the low frequency
temperature operation of the fuel cell down to 370 ◦ C.
arc relating to the gas exchange rate on the electrode, as reflected in the
To further investigate the effect of electrochemical reaction over
tiny contributions of the high frequency stages and the dominant
L0.8N0.2NCA anode on polarization resistance (Rp), the Rp of the syn­
contribution of the low frequency process. For the fuel cell with LNCA
thesized different anode materials were compared. The interfacial Rp
anode, there are three characteristic peaks (P1, P3 and P4) detected at
relating to charge transfer process and gas diffusion within the electrode
550 ◦ C in Fig. 4(e). The bulk resistances can be obtained from the
pores and gas adsorption/dissociation on TPB [49]. Combined with the
impedance spectra at the starting point of high frequency arc P1 (6.8 ×
results of DRT, polarization process is regarded as important basis for
10− 4 s), which is attributed to the grain-boundary arc of the ionic con­
measuring the catalytic activation on electrode [14,50]. The fuel cell
duction in CeO2 [47]. The middle and low frequency arcs P3 and P4
with L0.8N0.2NCA anode exhibited the lowest Rp (0.425 Ω cm2) at
represent the electrode processes of the electrochemical reactions and

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L. Huang et al. Applied Energy 336 (2023) 120788

Fig. 6. XRD patterns of anodes with LNCA and L0.8N0.2NCA before and after being subjected to H2 reduction (r-LNCA, r- L0.8N0.2NCA) (a), cross-sectional view of the
tested cell (b), SEM images of LNCA (c) and L0.8N0.2NCA (d) anode materials after being subjected to H2 reductive environment.

550 ◦ C, which is significantly lower than that obtained from the fuel cell same test under hydrogen gas reductive atmosphere, the diffraction
using LNCA anode (0.584 Ω cm2). The Rp values were comparable to the peaks of LNCA was still observed, indicating that it maintained the
recently reported active anode under similar conditions (H2/air feeds) layered metal oxide structure under the operation environment. This
such as LiNiO3-Li2CO3 (2.2 Ω cm2 at 550 ◦ C) and SrMo0.9Co0.1O3-δ (2.47 could be attributed to the low degree of mixing of Li+/Ni2+ in the more
Ω cm2 at 850 ◦ C) [51,52]. In addition, Rp of fuel cells exhibited an ordered layered structure of L0.8N0.2NCA [21]. Meanwhile, pinning ef­
Arrhenius dependance, and the corresponding catalytic activity of anode fect of doped Na may improve the structural stability of layered metal
can be compared by calculating the slope in Fig. 5(b). The activation oxides [48]. The reduction product of Ni particles formed on the surface
energies for the total polarization process were 0.41 eV for L0.8N0.2NCA of LNNCA could also increase the contact area between the electrode
anode, which is much lower than that for LNCA (0.70 eV). The polari­ and the fuel gas.
zation resistance includes the combined catalytic reactions of anode and Fig. 6(b) shows the cross-sectional view of Ni-LNNCA/CeO2/LNCA-
cathode. In order to further verify the catalytic activity of the anode, a Ni fuel cell after operating at 550 ◦ C in H2/air atmosphere, three distinct
fuel cell configuration using LNCA as both anode and cathode, and that layers can be obviously observed. The porous sublayer is a Ni-LNNCA
using L0.8N0.2NCA as both anode and cathode, and with H2 feeding to anode with a thickness of approximately 350 μm, and the dense inter-
both anode and cathode sides, were further compared at 550 ◦ C. The layer is CeO2 electrolyte membrane with a thickness of around 550
Nyquist curves obtained from these two systems were shown in Fig. 5(c). μm. Fig. 6(c) and (d) shows the SEM images for the morphological
The anode polarization resistance Rp-A can be estimated by the half of Rp change of the LNCA and L0.8N0.2NCA anode materials after fuel cell
despite of electrolyte and wire resistance in the symmetrical electrode testing. The LNCA could not maintain pristine layered structure and was
cell configuration. The Rp-A of LNCA and L0.8N0.2NCA symmetrical cell transformed into small particles with the loss of Ni ions which were
are 0.264 and 0.183 Ω cm2 at 550 ◦ C, indicating that the Na doping had reduced by H2 to Ni metal particles at the high temperature under the
effectively improved the catalytic activity on the LNNCA electrode. hydrogen reductive environment as shown in Fig. 6(c). The internal
strain caused by the phase transition could result in the collapse of the
layered structure, which in turn may make the electrical contact loss of
3.3. Comparison of cell components before and after test
the electrode materials. In contrast, the L0.8N0.2NCA still maintained the
basic appearance of polyhedron as shown in Fig. 6(d), and the Ni
In order to further investigate the stability of Na modified layer
nanoparticles grown in situ on the surface of L0.8N0.2NCA increased the
structured LNNCA anode, the pristine and Na doped electrodes before
contact area between the electrode and the fuel [23].
and after fuel cell testing (i.e., being subjected to H2 reductive envi­
Fig. 7(a) and (b) display the SEM images for the morphological
ronment) were analyzed by XRD as shown in Fig. 6(a). It has been found
change of the electrolyte material CeO2 collected at the interface of
that the LNCA anode has been reduced to Ni metal at the high temper­
anode and electrolyte. The pristine CeO2 particles are aggregated
ature under hydrogen gas reductive atmosphere, and no obvious LNCA
together, mostly display a spherical-like shape with about 50–100 nm
diffraction peak can be detected. In contrast, although the main
particles size distribution. In addition, the atomic contents of Ce and O
diffraction peak is also the metal Ni for L0.8N0.2NCA anode after the

8
L. Huang et al. Applied Energy 336 (2023) 120788

Fig. 7. SEM images and EDX analysis of CeO2 before (a) and after (b) the fuel cell test; (c) XRD patterns and (d) FTIR spectra of CeO2 before and after the fuel
cell test.

approaching 1:2 ratio, which is consistent with the chemical formula. maintained a stable cubic phase after fuel cell test, without noticeable
After the fuel cell test, it was found that CeO2 particles being coated with phase transition. For the FTIR spectra shown in Fig. 7(d), the peak
tiny particles on the surface. Meanwhile, the gaps between CeO2 parti­ located at 3432 cm− 1 could be attributed to the O–H band of the
cles were filled, and the fair density of the CeO2 electrolyte membrane as adsorbed H2O [24]. The strong peaks at 1438 and 864 cm− 1 in the FTIR
shown in Fig. 7(b) sustained a good gas-tightness ensuring the high OCV spectrum of CeO2 after fuel cell test are assigned to the C–O asymmetric
and power density of the fuel cell [22]. Na element was detected with an and symmetric stretching modes of Li/Na carbonate [53]. The peak
atomic content of 2.64%. Moreover, the atomic content of Ce and O were located at 996 cm− 1 could be attributed to the O–H band in absorbed
23.15% and 51.08%, with the amount of O increased significantly. LiOH [54], and the peak at 621 cm− 1 could be attributed to NaOH [55].
Combined with the results of recent reports about LNCA electrode [24], Several literatures reported that mixed carbonates could facilitate ion
we speculate that the excess oxygen may exist in the form of hydroxide transporting at low operation temperature for SOFC. Bodén et al. [56]
and carbonate products of Li and Na in CeO2 electrolyte membrane. The reported that the melting point of mixed carbonate (LiNaCO3) is about
XRD and FTIR data of the CeO2 material before and after the fuel cell 490 ◦ C, which is insufficient to maintain the fuel cell operation at
testing are shown in Fig. 7(c) and (d), it can be seen that the CeO2 still 370 ◦ C. Compared to LiOH (with a melting temperature at 471 ◦ C), the

9
L. Huang et al. Applied Energy 336 (2023) 120788

Fig. 8. Schematic illustration of the anode reaction and proton diffusion channels for the fuel cell with the LNNCA anode.

introduced NaOH with a lower melting temperature (318 ◦ C) could for designing a high-performance electrode for a next generation lower
contribute to the low temperature operation of the fuel cell [35]. temperature solid oxide fuel cell, i.e., protonic ceramic fuel cell.
Fig. 8 displays the schematic mechanism of the fuel cell operation
with LNNCA anode. The electrochemical oxidation of H2 on the surface
of LNNCA anode could be divided into several steps: (i) H2 molecular is CRediT authorship contribution statement
splitted into single H atom by LNNCA anode; (ii) with the presence of Na
induced influent oxygen vacancies, the pinning effect of the doped Na+ Liwen Huang: Data curation, Formal analysis, Writing – original
plays a vital role in maintaining the skeleton stability of LNNCA by draft. Jia Wang: Formal analysis. Wen-Feng Lin: Formal analysis,
decreasing Li+/Ni2+ intermixing, and dissociation of adsorbed hydrogen Writing - review and editing. Yan Wu: Project administration,
on the surface of anode might be effectively optimized; (iii) a portion of Supervision.
LNNCA at anode reduced into metallic Ni by H2, and the reduction
products Ni particles in-situ growth on the surface of LNNCA increasing Declaration of Competing Interest
the contact area between the electrode and the fuel gas. Meanwhile, the
low melting products modified the interface of anode and electrolyte, The authors declare that they have no known competing financial
which could optimize the contact interface of the anode and the elec­ interests or personal relationships that could have appeared to influence
trolyte at the three-phase boundaries, leading to a lower polarization the work reported in this paper.
resistance. Hence, the Na doping strategy provides a facile approach to
modify anode, and it could also be applied in other electrolytes to Data availability
achieve highly efficient performance at low temperatures.
Data will be made available on request.
4. Conclusion
Acknowledgements
Doping strategy was employed for improving anode with enhanced
the HOR catalytic activity and proton conductivity, to realize solid- The authors acknowledged the funding support from National Nat­
conducting ceramic fuel cells operated at relative low temperatures. In ural Science Foundation of China (NSFC, Grant No. 51774259), the UK
this work, the Na element was employed to dope the layered structure EPSRC (EP/W03784X/1), and the Royal Society via the Newton Fund
LNCA anode electrode achieved a maximum power density of 884 mW (NAF\R1\191294).
cm− 2 with H2 as fuel cell at 550 ◦ C, which is 1.6 times higher than that
obtained from the pristine LNCA anode. The Rp of L0.8N0.2NCA and
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