Fuel Processing Technology 235 (2022) 107380

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Fuel Processing Technology

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Ammonia as a green energy carrier: Electrochemical synthesis and direct

ammonia fuel cell - a comprehensive review
Bin Wang a, Tao Li a, *, Feng Gong a, Mohd Hafiz Dzarfan Othman b, c, Rui Xiao a, *
a
MOE Key Laboratory of Energy Thermal Conversion & Control, School of Energy and Environment, Southeast University, Nanjing 210096, China
b
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, Skudai 81310, Johor, Malaysia
c
Department of Energy Engineering, School of Chemical and Energy Engineering (FCEE), Universiti Teknologi Malaysia, Skudai 81310, Johor, Malaysia

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

Keywords: To achieve carbon neutrality by 2050 is an emergent challenge facing the world in order to tackle the climate
Ammonia change. Ammonia, being one of the most promising media for hydrogen storage, is regarded as an ideal carbon-
Electrochemical synthesis free energy carrier. Moreover, ammonia exhibits critical superiority in long-distance transportation and storage,
Fuel cell
which are the essential bottlenecks yet to be solved for hydrogen. Furthermore, the electrochemical synthesis of
Reversible solid oxide cell
‘green ammonia’ from renewable energy and its efficient utilization to generate electricity can be well integrated
with reversible solid oxide cell (R-SOC), which is a promising technology that provides a potential route to
decarbonize a number of applications dependent on fossil fuels. For electrochemical ammonia synthesis using
both solid oxide electrolytic cell (SOEC) and proton ceramic electrolytic cell (PCEC), the state-of-the-art
ammonia production rate can reach 8–9 × 10− 9 mol s− 1 cm− 2 at temperatures as low as 400 ◦ C. For direct
ammonia conversion using solid oxide fuel cell (SOFC) and proton ceramic fuel cell (PCFC), the best power
density reported is comparable to that of the hydrogen fuel cells, reaching >1.2 W/cm2. This review aims to
provide a comprehensive summary of the latest advances in both aspects: electrochemical ammonia synthesis
(also known as electrochemical Haber-Bosch Process) and direct ammonia fuel cells. The process mechanisms of
two major types of electrochemical routes based on oxygen ion conductor and proton conductor have been
reviewed, with a discussion on material development and stability issues.

1. Introduction
Renewable energy (wind, solar, tidal, biomass, etc.) plays an
increasingly critical role as the world moves towards carbon neutrality
[1]. However, they are often considered unreliable due to their inter­
mittent nature, as well as considerable dependence on external
geological and environmental constraints [2]. Therefore, a peak-shaving
technology is urgently needed to be integrated with renewable energy to
complete the smooth transmission. Hydrogen is one of the most prom­
ising carbon-free energy carrier [3]. However, its storage and trans­
portation remain critical challenges. On the other hand, the concept of
hydrogen carrier that is easy to store and transport has been proposed,
among which ammonia has been widely studied as a carbon-free
hydrogen carrier [4].
Ammonia is a chemical intermediate with a huge global annual
output of >160 million tons [5], most of which is used in the manu­
facture of fertilizer. Ammonia and its derivatives are also widely
adopted in pharmaceutical, synthetic fibers, resins and other fields [6].
Each ammonia molecule carries three hydrogen atoms, which can not
only be decomposed into hydrogen for various hydrogen energy utili­
zation, but also be directly used as the fuel for power generation [7]. The
volumetric energy density of liquid ammonia (12.9 MJ/L) is much
higher than that of liquid hydrogen (8.6 MJ/L), with superior hydrogen
storage capacity (121 kg-H2/m3 versus 70.8 kg-H2/m3) [4]. In terms of
storage and transportation, ammonia is far superior as it can be easily
liquefied at mild conditions (ambient temperature of about 10 atm or
atmospheric pressure of − 33 ◦ C), far milder than the condition of
hydrogen liquefaction [8].
The industrial synthesis of ammonia has been dominated by the
Haber-Bosch (H-B) process since 1910s, which typically requires tem­
peratures between 325 and 525 ◦ C, high pressures of 150–350 atm and
iron-based catalysts. Substantial studies have been carried out to further
improve the H-B process [9], including new catalysts, optimized reac­
tion processes, etc. However, it is extremely energy intensive due to the

* Corresponding author.
E-mail addresses: tao-li10@seu.edu.cn (T. Li), ruixiao@seu.edu.cn (R. Xiao).

https://doi.org/10.1016/j.fuproc.2022.107380
Received 30 April 2022; Received in revised form 15 June 2022; Accepted 20 June 2022
Available online 5 July 2022
0378-3820/© 2022 Elsevier B.V. All rights reserved.
B. Wang et al.
harsh reaction conditions. In addition, most hydrogen is sourced from
natural gas, leading to high carbon emissions [10]. Therefore, some new
synthesis techniques of ammonia have been proposed, including elec­
trochemical method, biological enzyme method, plasma method, pho­
tocatalytic method, etc., among which the electrochemical route can be
well integrated with the aforementioned clean renewable power and is
therefore considered as a green method with great potential [11,12].
The combination of green ammonia production and efficient ammonia
utilization is the focus of current ammonia energy research, which will
be comprehensively discussed in this review.
The reversible solid oxide cell (R-SOC) system can be applied for
both aspects of efficient synthesis and utilization simultaneously (See
Fig. 1), which are very similar in terms of system design, material
criteria, development bottlenecks, etc., and the combination of these
two technologies has demonstrated marked energy storage potential in
the future. However, most of the previous reviews [2,6,13,14] focus only
on one aspect, which is not convenient for readers to intuitively and
clearly understand ‘NH3-R-SOC’ as a bridging technology connecting
sustainable energy generation and efficient storage. Therefore, it is
needed to review these two technologies as a whole: the application of
R-SOC in electrochemical ammonia synthesis and direct ammonia fuel
cells at the same time. Here, the first half of the review systematically
introduces the electrochemical ammonia synthesis using both solid
oxide electrolytic cell (SOEC) and proton ceramic electrolytic cell
(PCEC). The working principle and the yield of ammonia synthesis
achieved from the latest material systems are also reviewed. The second
half introduces direct ammonia fuel cell in the form of both solid oxide
fuel cell (SOFC) and proton ceramic fuel cell (PCFC). In addition to the
current materials system and the power density achieved, the thermal
dynamics of ammonia decomposition at anode and the durability related
issues are also summarized.
Fig. 1. The framework of ammonia as an energy carrier.
2
Fuel Processing Technology 235 (2022) 107380
2. SOEC/PCEC electrochemical ammonia synthesis
At present, the common ammonia synthesis methods include ther­
mochemical, electrochemical, biochemical and photochemical routes,
etc. Their advantages and disadvantages are shown in Table 1.
Electrochemical ammonia synthesis is a process that nitrogen mol­
ecules are activated by electric energy to promote the non-spontaneous
nitrogen reduction reaction (NRR), and then react with the provided
electrons and hydrogen to produce ammonia [14]. The key feature of the
electrochemical synthesis route is the capability of using water as the
hydrogen source, which can significantly reduce energy consumption
and thus carbon emissions. Therefore, it is considered as an
environmentally-benign process and its conversion rate is not limited by
thermodynamic equilibrium [15]. Despite some unique advantages,
there are some critical limitations that hinder its widespread use. Ni­
trogen is inert with low NRR activity. In addition, the voltage of NRR is
similar to that of the hydrogen evolution reaction (HER), leading to
competitive side reactions and lowers the ammonia yield [16]. In order
to achieve high selectivity of NRR, some new methods have been used
for electrochemical ammonia synthesis, such as plasma method and
electrothermal chemical cycle method [17]. In addition, designing new
catalysts is a more common approach. At present, the catalysts used for
electrochemical ammonia synthesis include noble metals (Au, Pd, Ru,
etc.), transition metal-based catalysts (oxides, nitrides, carbides, single
atoms, etc.), carbon based catalysts, phosphorus based catalysts, etc.
Various design strategies have also been attempted to increase the active
sites and change the electronic structure of catalysts, such as manipu­
lating the size and morphology of particles, doping heteroatoms, intro­
ducing defects, organometrics, etc. [15,18]. However, no catalyst has
been able to make substantial progress in the commercialization of
electrochemical ammonia synthesis, and more efforts are needed to
design more effective catalysts.
B. Wang et al. Fuel Processing Technology 235 (2022) 107380

Table 1
Comparison of different ammonia synthesis routes [14].
Methods Temperature Pressure N2/H2 source Advantages Disadvantages
(◦ C) (MPa)

H-B process 325–525 15–35 N2 (air separation)/H2 (CH4 • Mature craftsmanship. • High energy consumption and
reforming) environmental pollution.
Thermocyclic 500–1300 ambient N2 (air separation)/H2O • No catalyst required; low cost. • High temperature.
Electrochemistry – ambient N2 (air separation)/H2 & H2O • H2O as hydrogen source. • Low Faradaic efficiency.
• A variety of routes. • Side reactinos (e.g. hydrogen evolution
• Capable of integration with reaction).
renewable energy.
Biochemistry ambient ambient N2/metal hydride • High electronic efficiency. • Slow reaction rate.
• Low energy consumption.
Photochemistry ambient ambient N2 (air separation)/H2O • Can be combined with solar energy. • Slow reaction kinetics.
• Clean and environmentally friendly.

Depending on the material selection, electrochemical ammonia
synthesis can be classified into aqueous electrolyte, molten salt elec­
trolyte and solid electrolyte, as shown in Table 2. Ammonia synthesis
using aqueous electrolyte is generally considered to be a simple and less
costly method because water can be used directly as the hydrogen
source. In order to avoid the oxidation of synthesized ammonia at the
anode, proton exchange membrane (PEM) is usually used to separate the
anode and cathode, such as Nafion membrane. However, the ammonia
synthesis rate and Faraday efficiency of aqueous electrolyte are low and
affected by the pH value of solution [16]. The temperature of molten salt
electrolyte is generally 300–500 ◦ C, which can be divided into molten
chloride salt, molten hydroxide salt and composite electrolyte. The
molten salt electrolyte has a strong ion transfer ability and a wide
electrochemical window to facilitate the adjustment of electrode po­
tential, so its Faraday efficiency and ammonia yield are high. However,
the molten salt is highly corrosive and the durability of the electrode is
poor [19]. Solid electrolyte can effectively inhibit the side reaction of
hydrogen evolution, thus helping to improve Faraday efficiency. A wide
range of temperatures have been reported from room temperature to
700–800 ◦ C [20]. This review focuses on the application of high tem­
perature solid electrolytes. Detailed descriptions of some of the other
types of electrolytes can be found in reviews by Zhao et al. [15]and
Firman et al. [14].
2.1. Working principle of SOEC/PCEC for ammonia synthesis
In the case of SOEC, as shown in Fig. 2 (a), a mixture of water vapor
and nitrogen is introduced to the cathode and react with an external
electron, resulting in ammonia and oxygen ions, which are transported
to the anode by the electrolyte to produce oxygen and electrons
(transported to the cathode by an external circuit). For PCEC, hydrogen
sources can be hydrogen, water vapor, hydrocarbons, etc. The reaction
mechanism with hydrogen and water vapor as hydrogen sources is
shown in Fig. 2 (b). When hydrogen is introduced to the anode, the
protons generated at the anode are transported to the cathode by an
electrolyte under an external current and react with nitrogen and elec­
trons to form ammonia. Water vapor works similarly, except that the
anode produces oxygen as well as protons.
Table 2
Comparison of Different Electrolytes in Electrochemical Synthesis of Ammonia
[15,19].
Electrolytes Advantages Disadvantages
Solid • Effective inhibition of • High requirements for
electrolytes hydrogen evolution reaction. related equipment.
• High Faraday efficiency. • High operating
• Fast reaction kinetics. temperature.
Molten salt • High ionic conductivity • Corrosion issue; poor
electrolytes • High current efficiency. durability.
Aqueous • Low temperature. • Slow reaction rate.
electrolytes • Simple and cost-effective. • Low Faraday efficiency.
2.2. Research progress of SOEC/PCEC for ammonia synthesis
2.2.1. Development of SOEC for ammonia synthesis
SOEC ammonia synthesis produces an useful by-product-pure oxy­
gen-on the anode side, which improves the economy of the process.
Unfortunately, oxygen ion conduction electrolytes generally require
high temperatures of 700–800 ◦ C or even higher to achieve ideal ionic
conductivity. Thus ammonia decomposition may occur at such high
temperatures leading to a decline in ammonia synthesis rate. Therefore,
studies on ammonia synthesis by SOEC are relatively rare. The few
studies to our best knowledge are summarized in Table 3. In 2009,
Skodra and Stoukides [21] used the most common yttria-stabilized zir­
conia (YSZ) as an electrolyte to synthesize ammonia. Pd was employed
as a cathode together with Ru attributed to its good H2O dissociation,
while the anode material was Ag. However, the performance of
ammonia synthesis by this reactor prototype was far from satisfactory, in
which ammonia generation was observed from 500 ◦ C and the rate of
production was increased by two orders of magnitude at 650 ◦ C. They
attributed this to Ru’s very poor electrical conductivity. Although an Ag
layer was used to improve the conductivity, the problem with this
electrode design was that a large proportion of the protons never
reached the surface of Ru, but instead bonded to form gaseous hydrogen
on the silver film. Although the performance is poor, it proves that SOEC
can be used in ammonia synthesis. In 2014, Jeoung et al. [22] used Pt ||
Ce0.9Gd0.1O2-δ (GDC) ||Pt button cell at 400–600 ◦ C under atmospheric
pressure and found that with the rise of temperature, the Faraday effi­
ciency showed a contrary trend to the efficiency of ammonia generation,
which could be attributed to the increase of competitive HER, thus
blocking the active site for nitrogen adsorption. The maximum ammonia
generation rate reported at 1.2 V and 600 ◦ C is 3.67 × 10− 11 mol s− 1
cm− 2.
The most recent study was carried out by Li et al. [23] in 2021.
Similarly, they used GDC as electrolyte, La0.33Sr0.67Cr1-xFexO3-δ (LSCrF)
and GDC were linked together to form a unique set of electrocatalytic
composites. On this basis, an in situ template was also invented, which
used a pore-forming agent with controllable size to optimize the pore
structure of the cathode and used for ammonia synthesis. In order to
improve the efficiency of ammonia synthesis, an optimized ball milling
method was developed to configure cathode composites with different
formulations in response to changes in operating voltage and tempera­
ture. A maximum ammonia formation rate of 3.0 × 10− 10 mol s− 1 cm− 2
was obtained at 600 ◦ C and 1.8 V, which was close to the performance of
proton conductive electrolyte under the same condition. They attributed
this superior performance to additional oxygen vacancy formed, high
interactions between catalysts and reactants, and gas channels through
large pore structures. From the number of studies and the performance
achieved, SOEC does not appear to be suitable for ammonia synthesis.
However, it is encouraging that the perovskite structure can generate
different functions through different doping, which is driving the
continuous improvement of the SOEC performance for ammonia syn­
thesis, and more research needs to be continued.

3
 B. Wang et al. Fuel Processing Technology 235 (2022) 107380

Fig. 2. Principle of SOEC/PCEC electrochemical synthesis of ammonia, (a): SOEC; (b): PCEC.

surface at a reaction rate that increases well beyond the ion flow rate
Table 3
(Faraday current) by orders of magnitude. This phenomenon has been
Summary of SOEC electrochemical ammonia synthesis.
studied in the field of solid electrolyte for ammonia synthesis. For
Electrolyte Electrode Cathodic Conditions Production Ref. example, Yokari et al. [29] used industrial iron catalysts for ammonia
(cathode// Flow Rate of
synthesis, and the reaction rate was greatly increased when protons
anode) Ammonia
(mol s− 1 were pumped to the catalyst surface by 13 folds. Garagounis et al. [30]
cm− 2) conducted a thermodynamic analysis of NEMCA for reactions with
GDC LSCrF- N2-H2O 1.8 V; 3.0 × 10− 10
[23]-
limited equilibrium conversion using the ammonia synthesis reaction as
GDC// (97:3 vol 600 ◦ C 2021 a model system, and revealed that the Faradaic efficiency may exceed
BCFN-GDC %) unity. This pioneering research went through different stages in the
11
GDC Pt//Pt N2-H2O 1.2 V; 3.67 × 10− [22]- following decades, focusing on the optimization of electrolyte and
600 ◦ C 2014
− 14 electrode materials, the selection of hydrogen source, etc., to achieve the
YSZ Pd-Ru//Ag N2-H2O 2 V; 1.0× 10 - [21]-
500–700 ◦ C 5.0× 10− 12 2009 purpose of improving ammonia production rate and Faradaic efficiency.
mol s− 1g−cat1 A summary of relevant studies is presented in Table 4.
Note: GDC: Ce0.9Gd0.1O2-δ; LSCrF: La0.33Sr0.67Cr1-xFexO3-δ; BCFN: BaCo0.7
Fe0.2Nb0.1O3-δ. 2.2.2.1. Development of electrolyte. The properties of the electrolyte
determine the rate of proton transfer between the electrodes, which in
2.2.2. Development of PCEC for ammonia synthesis turn affects the activity of the PCEC to synthesize ammonia. The elec­
In terms of electrochemical ammonia synthesis, PCEC is more pref­ trolyte material should possess high proton conductivity to reduce
erable ascribed to the features of lower temperature required, better ohmic loss, as well as negligible electrical conductivity. In addition,
proton conductivity and lower activation energy. In 1981, Iwahara et al. good mechanical and chemical stability are necessary in long-term
[24] reported that doped SrCeO3-based perovskite compounds displayed operation. It has been well accepted that the reaction rate of ammonia
proton conductivity in hydrogen-containing atmosphere or water vapor synthesis depends on proton conductivity of the electrolyte. Yoo et al.
at elevated temperatures, and subsequently demonstrated the produc­ [54] summarized the effect of the proton conductivity of Ba (Ce, Zr, AE,
tion of hydrogen via water vapor electro-deposition. Further in­ RE) O3-δ and (La, AE) (Ga, Mg)O3-δ perovskite-type and (Ce, RE)O2− δ
vestigations on different types of perovskites and dopants have been and (La, Ca)2 (Zr, Ce)2O7− δ fluorite-type oxide electrolytes (AE = alka­
conducted, such as rare earth metal doped BaCeO3 and in-doped line earth elements and RE = rare-earth elements) on the rate of
CaZrO3, etc. [25,26]. ammonia synthesis, as shown in Fig. 3. After fitting the relevant data, an
Although oxides with proton conductivity have been extensively empirical relationship was obtained, as shown in the Eq. (1). It could be
adopted as fuel cell electrolytes or hydrogen separation membranes, it seen that the ammonia production rate shows a proportional relation­
was not until 1998 when Marnellos and Stoukides first proposed the ship with proton conductivity, suggesting that the proton conductivity
electrochemical ammonia synthesis using high-temperature proton of the electrolyte can be used to predict the ammonia production rate
conductive solid electrolyte [27]. The electrolytic cell they used when bimetallic Ag-Pd is used as the cathode electrocatalyst, which
included SrCe0.95Yb0.05O3− α (SCY) electrolyte sandwiched between two provides certain guidance in material design. The ohmic loss of elec­
palladium electrodes (Pd ||SCY|| Pd). Nitrogen and hydrogen were fed trolyte of proton conductors is related to factors such as temperature,
into the cathode and anode, respectively. At 570 ◦ C, an ammonia syn­ thickness of electrolyte layer and preparation method of electrolyte
thesis rate of approximately 3 × 10− 9 mol s− 1 cm− 2 could be achieved, materials [55]. In general, higher working temperature not only leads to
with 78% of the protons converted to ammonia, which was more than improved proton conductivity, but also the the probability of ammonia
three orders of magnitude higher than conventional catalytic reactors decomposition. Thus, the optimal temperature should be comprehen­
(CCR) at atmospheric pressure. In contrast, CCR required a pressure of sively evaluated. Reducing the thickness of the electrolyte layer is
106 bar if it was to achieve similar performances, which showed that the another effective approach to reduce ohmic loss, but the design should
use of PCEC for ammonia synthesis can enable milder conditions than be either electrode-supported or external supported to ensure the me­
the traditional high-pressure process. Marnellos et al. [28] further chanical robustness. For the preparation method, there are currently two
improved such electrolytic cell design and proposed the phenomenon of methods for synthesizing high-temperature proton conductors: high-
Non-Faradaic Electrochemical Modification of Catalytic Activity temperature solid-phase reaction method and sol-gel method. In addi­
(NEMCA). When applying certain current or voltage to the solid elec­ tion, other wet chemical methods such as hydrothermal method,
trolyte cell, the solid electrolyte pumps out ions and excites the catalyst coprecipitation method, Pechini method, citrate method and

4
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 B. Wang et al. Fuel Processing Technology 235 (2022) 107380

Table 4 Table 4 (continued )

Summary of PCEC electrochemical ammonia synthesis. Electrolyte Electrode Gas feed Conditions Production Ref.
Electrolyte Electrode Gas feed Conditions Production Ref. (cathode// (cathode// Rate of
(cathode// (cathode// Rate of anode) anode) Ammonia
anode) anode) Ammonia (mol s− 1
(mol s− 1 cm− 2)
cm− 2)
1 × 10− 9-4 [28]-
BCZG-2.5L (2K,10Fe)- N2//3 vol 500 ◦ C, 0.8 V 1.87 × [31]- × 10− 9 2000
Ni-BCZG// % H2O + 10− 10 2020 SCY Pd //Pd N2//H2 570 ◦ C 3 × 10− 9 [27]-
Ni-BCZG H2 1998
9
BZCY81 VN-Fe// N2//CH4 600 ◦ C, 0.63 1.89 × 10− 9
[32]- LSGM Ag-Pd// N2//H2 550 ◦ C 2.37 × 10− [49]-
Ni-BZCY72 + H2O V 2020 Ag-Pd 2007
9
BCZY BSTR//Ni- N2//H2O 500 ◦ C, 1.2 V 1.1 × 10− 9
[33]- LBGM Ag-Pd// N2//H2 520 ◦ C 1.89 × 10− [50]-
BCZY + H2 2019 Ag-Pd 2008
BZCY72 Ni- H2 + N2// 620 ◦ C, 2.4 V, 4.1 × 10− 9
[34]- LCZO1 Ag-Pd// N2//Wet 520 ◦ C, 0.8 V 2 × 10− 9
[51]-
BZCY72// H2 H2/N2 = 1.0 2016 Ag-Pd H2 2005
9
Cu- N2//H2 620 ◦ C, 2.4 V 1.7 × 10− 9 LCCO Ag-Pd// N2//Wet 520 ◦ C, 0.8 V 1.3 × 10−
BZCY72 Ag-Pd H2
BZCY72 Ni- N2//H2 550 ◦ C, 2.1 V, 2.9 × 10− 9
[35]- LCZO2 Ag-Pd// N2//Wet 520 ◦ C 1.76 × 10− 9
[52]-
BCZY27// PH2/PN2 = 1.0 2015 Ag-Pd H2 2004
− 9
Rh LDC Ag-Pd// N2//Wet 650 ◦
C, 0.8–1 7.2 × 10 [53]-
BCZYZ Pd-25Fe- N2//3% 450 ◦ C 4 × 10− 9
[36]- Ag–Pd H2 V 2006
9
BCZYZ// H2O + 4% 2017 YDC Ag-Pd// N2//Wet 650 ◦
C, 0.8–1 7.5 × 10−
25Ni10Ce- H2 in Ar Ag-Pd H2 V
9
BCZYZ GDC Ag-Pd// N2//Wet 650 ◦
C, 0.8–1 7.7 × 10−
Ru-25Fe- N2//3% 500 ◦ C 2.6 × 10− 9 Ag-Pd H2 V
9
BCZYZ// H2O + 4% SDC Ag-Pd// N2//Wet 650 ◦
C, 0.8–1 8.2 × 10−
25Ni10Ce- H2 in Ar Ag-Pd H2 V
BCZYZ
9 Note: BCZG-2.5 L: BaCe0⋅7Zr0.1Gd0.2O3-δ-2.5 wt% Li2CO3; BZCY81: BaZr0.8
25Fe- N2//3% 400 ◦ C 2.9 × 10−
BCZYZ// H2O + 4% Ce0.1Y0.1O3; BZCY72: BaZr0.7Ce0.2Y0.1O3-a; BCZY: BaCe0.4Zr0.4Y0.2O3; BSTR:
25Ni10Ce- H2 in Ar Ba0.5Sr0.5Ti0.9Ru0.1O3-δ; BCZYZ: BaCe0.5Zr0.3Y0.16Zn0.04O3-δ; BCY15:
BCZYZ BaCe0.85Y0.15O3− α; BSCF: Ba0.5Sr0.5Co0.8Fe0.2O3− α; BCY: BaCe1− xYxO3− α; BCYR:
BCY15 Ag-Pd- N2//Wet 530 ◦ C 4.1 × 10− 9
[37]- Ru-doped BaCe0.9Y0.1O3− α; LSTR: Ru-doped La0.3Sr0.6TiO3; BCC:
BSCF//Ni- H2, PH2O = 2010 BaCe1− xCaxO3− α; BCD: BaCe1− xDyxO3− α; BCS: BaCe0.90Sm0.10O3− δ; BCGS:
BCY15 0.023 atm BaCe0.80Gd0.10Sm0.10O3− δ; BCGO: BaCe1-xGdxO3-α; BCN18: Ba3(Ca1.18Nb1.82)O9;
BCY (NiO) Ni-BCYR// N2//2.3 500 ◦ C, − 0.6 5.30 × [38]- BCZN: Ba3CaZr0.5Nb1.5O9; BCNN: Ba3Ca0.9Nd0.28Nb1.82O9; SCY:
Ni-BCY vol% H2O V (vs OCV) 10− 10 2017
SrCe0.95Yb0.05O3− α; LSGM: La0.9Sr0.1Ga0.8Mg0.2O3− α; LBGM: La0.9B­
+ H2
BCY (NiO) Ni-BCY// N2//2.3 500 ◦ C, − 0.2 3.36 × [39]-
a0.1Ga1–xMgxO3–α. LCZO1: La1.95Ca0.05Zr2O7− δ; LCCO: La1.95Ca0.05Ce2O7− δ;
Ni-BCY vol% H2O V (vs OCV) 10− 10 2017 LCZO2: La1.9Ca0.1Zr2O6.95; LDC: Ce0.8La 0.2O2− δ; YDC: Ce0.8 Y 0.2O2− δ; GDC:
+ H2 Ce0.8Gd 0.2O2− δ; SDC: Ce0.8Sm 0.2O2–δ.
9
BCY Ag-Pd// N2//Wet 500 ◦ C 2.1 × 10− [40]-
Ag-Pd H2 2009
11
BCY Ni-BCYR// 2% H2O + 500 ◦ C, − 0.3 1.1 × 10− [41]-
Pt 98% N2// V (vs OCV) 2017
2% H2O +
20% H2 +
78% Ar
12
BCY LSTR- 2.3% H2O 500 ◦ C, − 0.1 3.8 × 10− [42]-
BCY//Pt + 98% V (vs OCV) 2016
N2//2.3%
H2O + 20%
H2 + 78%
Ar
9
BCC Ag-Pd// N2//Wet 480 ◦ C 2.69 × 10− [43]-
Ag-Pd H2, PH2O = 2010
0.023 atm
9
BCD Ag-Pd// N2//Wet 530 ◦ C 3.5 × 10− [44]-
Ag-Pd H2, PH2O = 2010
0.023 atm
9
BCS Ag-Pd// N2//H2 620 ◦ C, 0.6 V 5.23 × 10− [45]-
9
BCGS Ag-Pd 5.82 × 10− 2007
9
BCGO Ag-Pd// N2//Wet 480 ◦ C 4.63 × 10− [46]-
Ni-BCGO H2 2009
9
BCGO Ag-Pd// N2//H2 480 ◦ C,0.8–1 3.09 × 10− [47]-
Ag-Pd V 2004
9
BCN18 Ag-Pd// N2//H2 620 ◦ C 1.42 × 10− [48]-
Ag-Pd 2005 Fig. 3. Proton conductivity dependence of the electrochemical ammonia for­
BCZN Ag-Pd// N2//H2 620 ◦ C 1.82 × 10− 9 mation rate for selected proton-conducting Ba(Ce,Zr,AE,RE)O3-δ and (La,AE)
Ag-Pd (Ga,Mg)O3-δ perovskite-type and (Ce,RE)O2− δ and (La,Ca)2(Zr,Ce)2O7− δ
9
BCNN Ag-Pd// N2//H2 620 ◦ C 2.16 × 10− fluorite-type oxide electrolytes using bimetallic Ag-Pd cathode electrocatalysts
Ag-Pd at temperatures of 350–650 ◦ C [54].
SCY Ru-Ag//Pd N2//H2O 650 ◦ C, 2 V 5.0× 10− 12 [21]-
mol s− 1g−cat1 2009
(appr.) microemulsion method have been applied to the fabrication of high
SCY Pd //Pd N2//H2 570 ◦ C temperature proton conductors.
log rNH3 = a + b log (σH + T) (1)

5
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B. Wang et al.
The proton conductive solid oxides explored by the current research
include perovskite, fluorite, pyrochlore, and polymer types. Perovskite
materials are widely used in the field of PCEC ammonia synthesis
because of the advantages of lattice oxygen defects induced through
element doping or structural defects, water absorption in a suitable
environment, and rapid migration of protons after forming [56,57]. Its
structure can be divided into two types, namely simple and complex
perovskite. Simple perovskite is generally a cubic structure with the
general formula of ABO3, where A and B denote cations. This structure
not only has a stable crystal structure, but also has a strong tolerance for
the variation of the ionic radius of A and B sites. Furthermore, the
structure can be tailored for enhanced proton conductivity and chemical
stability via doping. On the other hand, the general formulas of complex
perovskite structures are A2(BC)O6 and A3(BC2)O9 [58]. For the proton
conduction mechanism, previous studies have proposed various theories
and models, such as defect theory, tunnel theory, primary model theory,
etc. [59].
Perovskite solid oxide electrolytes currently used for ammonia syn­
thesis include SrCeO3, LaCaO3, CaZrO3, SrZrO3, BaCeO3 and other types.
The relevant cell structures, testing conditions, and production rates are
summarized in Table 4. SrCeO3-based material is among the earliest to
be tested for SOEC ammonia synthesis. As mentioned above, Marnellos
and Stoukides [27] doped Yb element at the B site of SrCeO3 to form
SCY, which was used as an electrolyte and achieved good performance
in ammonia synthesis, proving the prospect of proton conductor elec­
trolyte in ammonia synthesis. However, there are few studies on
ammonia synthesis using SrCeO3-based materials. Skodra et al. [21] also
used SCY as electrolyte, Ru-Ag and Pd as cathode and anode respec­
tively, and obtained an ammonia production rate of about 5.0× 10− 12
mol s− 1g−cat1 at 650 ◦ C and 2 V. Although this performance is poor, it is
worth noting that the anode gas they used is H2O. In subsequent
development, LaCaO3 based materials are often used, and doped ele­
ments include Sr, Mg, Ba, Ca, etc. [49,50]. Chen et al. [60] studied the
capacity of La0.9M0.1Ga0.8Mg0.2O3− δ (M = Ca2+, Sr2+, Ba2+) as an
electrolyte for ammonia synthesis, in which Sr doping has the highest
ammonia production rate, reaching 2.53 × 10− 9 mol s− 1 cm− 2 at 520 ◦ C.
Besides, In-doped CaZrO3 [29] and Y-doped SrZrO3 [61] have also been
tried to be applied to SOEC ammonia synthesis due to their better
chemical stability.
The above materials are not mainly used in current research, instead
BaCeO3-based materials are basically used in PCEC ammonia synthesis
in recent years. Y doping is the most widely used. Shimoda et al. [39]
adopted BaCe0.9Y0.1O3-δ (BCY) mixed with NiO as electrolyte and Ni-
BCY as cathode and anode, which could achieve ammonia production
rate of 3.36 × 10− 10 mol s− 1 cm− 2 at 500 ◦ C. Similarly, Kobayashi et al.
[38] adopted the same structure, except that the cathode was changed to
BaCe0.8Y0.1Ru0.1O3-δ (BCYR), which also achieved ammonia production
rate of 5.30 × 10− 10 mol s− 1 cm− 2 at 500 ◦ C, proving that cathode
doping with Ru can effectively improve the reaction activity. The doping
amount of Y is also a key factor affecting the proton conductivity of BCY.
Guo et al. [40] prepared BaCe1− xYxO3− α (x = 0.05, 0.10, 0.15, 0.20) via
a micro-emulsion method and constructed an electrolytic cell for
ammonia synthesis using Ag-Pd electrode. The results showed that, the
ammonia production rate reached 2.1 × 10− 9 mol s− 1 cm− 2 at 500 ◦ C
when x = 0.15. Subsequently, BaCe0.85Y0.15O3-δ (BCY15) was applied to
an electrolytic cell with Ag-Pd-Ba0.5Sr0.5Co0.8Fe0.2O3− α (BSCF) cathode
and Ni-BCY15 anode, achieving an ammonia production rate of 4.1 ×
10− 9 mol s− 1 cm− 2 at 530 ◦ C, which is an order of magnitude higher than
the above doping amount of 0.1 [37]. Ca and Dy have also been tried to
dope BaCeO3-based materials, and the synthetic ammonia performance
is comparable to Y. Wang and Liu et al. [43,44] prepared
BaCe0.9Ca0.1O3− α (BCC) and BaCe0.85Dy0.15O3− α (BCD) via a micro­
emulsion process for the electrolyte, while Ag-Pd was used as the elec­
trode, and ammonia production rates of 2.69 × 10− 9 mol s− 1 cm− 2 and
3.5 × 10− 9 mol s− 1 cm− 2 were achieved at 480 ◦ C and 530 ◦ C, respec­
tively. Also using Ag-Pd as electrode, Sm-doped BaCeO3 was used as
6
Fuel Processing Technology 235 (2022) 107380
electrolyte in the form of BaCe0.90Sm0.10O3− δ (BCS), achieving an
excellent ammonia synthesis performance of 5.23 × 10− 9 mol s− 1 cm− 2
at 620 ◦ C [45].
In order to further improve the ammonia synthesis ability of BaCeO3-
based materials, double doping and even multiple doping were
employed. In the above-mentioned BCS, Li et al. [45] further doped Gd
to form BaCe0.80Gd0.10Sm0.10O3− δ (BCGS), and the ammonia production
rate was slightly improved to 5.82 × 10− 9 mol s− 1 cm− 2 at 620 ◦ C. The
double doping of BaCeO3 by Zr and Y is also an often studied strategy,
and Vasileiou et al. synthesized double-doped BaZr0.7Ce0.2Y0.1O2.9
(BZCY72) electrolyte. It was first used for ammonia synthesis in a single-
chamber cavity, and with Ni-BCZY27 and Rh as cathode and anode,
respectively, the performance of 2.9 × 10− 9 mol⋅s− 1 could be achieved
at 550 ◦ C and 2.1 V [35]. Subsequently, they also used BZCY72 as the
electrolyte, Ni-BZCY72 and Cu-BZCY72 as the cathode and anode,
respectively, to synthesize ammonia in a dual-chamber reactor.
Comparing the situation of feeding different gases to the cathode, it was
found that when pure nitrogen and pure hydrogen was fed to the cath­
ode and anode respectively, the rate of 1.7 × 10− 9 mol s− 1 cm− 2 could be
achieved at 620 ◦ C and 2.4 V, while when the cathode gas was changed
to H2/N2 = 1.0, 4.1 × 10− 9 mol s− 1 cm− 2 could be obtained under the
same conditions [34]. In a recent study, Lei et al. [31] synthesized
BaCe0⋅7Zr0.1Gd0.2O3-δ (BCZG) using a citrate sol-gel method, with (2 K,
10Fe)/Ni-BCZG cathode and Ni-BCZG anode, respectively. As shown in
Fig. 4, the incorporation of 2.5 wt% Li2CO3 could reduce the sintering
densification temperature to 1250 ◦ C, and BCZG-2.5 L could achieve 1.9
× 10− 2 S cm− 1 total ionic conductivity at 600 ◦ C in wet hydrogen at­
mosphere, which was higher than the same electrolyte without doping
[62]. Furthermore, in the tests of ammonia synthesis, the maximum
ammonia production rate was 1.87 × 10− 10 mol s− 1 cm− 2 and the
maximum current efficiency was 0.53% at applied voltage of 0.8 V and
500 ◦ C. Klinsrisuk et al. [36] carried out triple doping of Zr, Y and Zn on
BaCeO3 to form BaCe0.5Zr0.3Y0.16Zn0.04O3-δ (BCZYZ) electrolyte, the
anode was 25Ni10Ce-BCZYZ, and the cathode was M-25Fe-BCZYZ (M =
Pd, Ru and none). Corresponding to the three cathode structures, 4 ×
10− 9 mol s− 1 cm− 2, 2.6 × 10− 9 mol s− 1 cm− 2, 2.9 × 10− 9 mol s− 1 cm− 2
were achieved at 450 ◦ C, 500 ◦ C, and 400 ◦ C, respectively. Although
multi-doping can reduce the operating temperature and increase the
ammonia production rate to a certain extent, it is not enough to have a
qualitative impact on the PCEC ammonia synthesis system, and more
research on materials is needed to promote its development.
Pyrochlore-type oxides have the general formula A2B2O7 and have
two types of cations (A3+ and B4+). Xie and his colleagues [51,52] tested
the performance of La2Zr2O7, La2Ce2O7, La1.9Ca0.1Zr2O6.95 as electro­
lytes for ammonia synthesis. Among them, La2Zr2O7 had the highest
performance, which could reach 2 × 10− 9 mol s− 1 cm− 2 at 520 ◦ C and
0.8 V when Ag-Pd was used as the electrodes, and the cathode and anode
were fed with dry nitrogen and wet hydrogen, respectively. Fluorite
structure oxides have the general formula AO2, where A is a large
tetravalent cation. According to the experiment conducted by Liu et al.
[53] on ammonia synthesis using fluorite structured oxides as electro­
lytes, it was found that its ammonia synthesis performance was even
higher than that of perovskite and pyroxite structured oxides. They
tested four types of fluorite structure oxides, Ce0.8La0.2O2− δ,
Ce0.8Y0.2O2− δ, Ce0.8Gd0.2O2− δ, Ce0.8Sm0.2O2− δ, respectively. The lowest
ammonia production rate could reach 7.2 × 10− 9 mol s− 1 cm− 2 when
Ag-Pd was used as electrodes and the cathode and anode were fed with
dry nitrogen and wet hydrogen, respectively.
2.2.2.2. Development of electrode. The electrode involves two electro­
chemical reactions at the anode and cathode, respectively. In the elec­
trochemical synthesis of ammonia by PCEC, the electrode needs to have
good proton and electron conduction characteristics, high catalytic
characteristics for nitrogen adsorption and ammonia desorption, and
long time operation stability. As shown in Table 4, Ag-Pd is the most
B. Wang et al.
Fig. 4. (a) Total conductivity curves in a wet hydrogen atmosphere for BCZG sintered at 1500 ◦ C and BCZG-xL (x = 2.5 and 5) sintered at 1250 ◦ C. (b): NH3
formation rates and current efficiencies at 500 ◦ C with different applied voltages, the electrolytic cell structure is (2 K, 10Fe)/Ni-BCZG||BCZG-2.5 L||Ni-BCZG
electrolytic cell [31].
widely used electrode material. Pd can promote the bonding force of
nitrogen when combined with hydrogen; whereas Ag can improve the
conductivity of electrode. In addition, Pt is also used as a electrode in
cells with BaZr0.8Y0.2O3− δ (BZY) electrolyte, but its ammonia production
rate is lower than 1 × 10− 12 mol s− 1 cm− 2, which may be attributed to its
high activity for HER [63]. Unfortunately, the high cost of noble metals
and poor thermal matching with electrolytes limit their large-scale ap­
plications [36].
Perovskite oxide is also used as electrode material because of its
simple synthesis, low cost and good catalytic performance. Moreover,
oxygen vacancies can be well introduced in lattice structure via doping
strategy, which could help improve the performance of the electrolytic
cell. Perovskite is more commonly used as a carrier for doping metal
components with high catalytic activity, which not only ensures high
catalytic activity, but also has the same component as electrolyte to
avoid incompatibility caused by high temperature. For example, Wang
et al. [37] used Ag-Pd-BSCF as the electrode material of an electrolytic
cell with BCY15 electrolyte, and obtained an excellent ammonia pro­
duction rate of 4.1 × 10− 9 mol s− 1 cm− 2 at 530 ◦ C. In addition to Ag and
Pd, Fe, Ru and Ni are often used as doping catalysts. The use of
BaZr0.1Ce0.7Y0.2O3-a (BZCY) proton conducting carrier has been shown
to increase the ammonia synthesis activity of Ni by an order of magni­
tude [64]. Due to Fe’s good catalytic ability in ammonia synthesis,
Klinsrisuk et al. [36] doped Fe into BCZYZ material to form a 25Fe-
BCZYZ electrode, and the ammonia production rate was 2.9 × 10− 9
mol s− 1 cm− 2 at 400 ◦ C. Ru has higher catalytic activity than Fe, which
can promote the dissociation of N–N bond more effectively [65]. Kim
et al. [33] used Ba0.5Sr0.5Ti0.9Ru0.1O3-δ (BSTR) as the cathode material,
feeding dry nitrogen and wet hydrogen respectively at the cathode and
anode. It was found that doping Ru at the B site of BST could improve its
electrochemical performance, because increasing the substitution of
Ru4+ for Ti4+ would lead to a decrease in ohmic resistance. The
maximum ammonia production rate could be 1.1 × 10− 9 mol s− 1 cm− 2
at 500 ◦ C and 1.2 V. Similarly, Kosaka et al. [42] also successfully
precipitated highly dispersed Ru nanoparticles with a size of 2–5 nm in
situ in La0.3Sr0.6TiO3 (LST) and used them for ammonia synthesis.
Further, the particle size and dispersion could be controlled by reduction
temperature and Ru doping amount.
2.2.2.3. Development of hydrogen sources. PCEC can synthesize
ammonia from many hydrogen sources. Hydrogen is the most studied,
but hydrogen often comes from reforming fossil fuels, leading to higher
energy consumption and higher carbon emissions. In the studies sum­
marized above, wet hydrogen is mostly used as a hydrogen source rather
7
Fuel Processing Technology 235 (2022) 107380
than hydrogen, where water vapor is used to ensure proton conduction
properties. The electrochemical ammonia synthesis by using H2O
instead of hydrogen as a hydrogen source in proton conductor was
successfully achieved by Stoukides et al. [21]. Using H2O can avoid the
production and purification costs of hydrogen, and oxygen can be pro­
duced as a byproduct, which greatly improves the economic perfor­
mance. Unfortunately, the use of H2O as hydrogen source will reduce the
rate of ammonia production to a certain extent [20]. Shimoda et al. [39]
studied the ammonia synthesis performance of electrolytic cell with Ni-
BCY|| BCY (NiO)||Ni-BCY structure under different gas supply, the
ammonia production rate of 3.36 × 10− 10 mol s− 1 cm− 2 could be ach­
ieved at 500 ◦ C and − 0.2 V when the gas supply was nitrogen and wet
hydrogen. However, it was only 2.79 × 10− 10 mol s− 1 cm− 2 at 500 ◦ C
and − 1.8 V when nitrogen and argon were supplied by water vapor.
Using hydrocarbons as a hydrogen source is also an option. Wang
et al. [66] were the first to use natural gas and nitrogen as raw materials
to synthesize ammonia in solid-state proton conductor cells. The elec­
trolyte used was Ce0.8Y0.2O1.9 (YDC)-(Ca3(PO4)2-K3PO4), which could
achieve the ammonia production rate of 6.95 × 10− 9 mol s− 1 cm− 2 at
650 ◦ C and 1.0 V. Similarly, in a recent study, Kyriakou et al. [32] in­
tegrated the production and purification of hydrogen and ammonia
synthesis into a VN-Fe||BaZr0.8Ce0.1Y0.1O3||Ni-BaZr0.7Ce0.2Y0.1O3-a
proton conduction membrane reactor. On the one hand, a mixture of
methane and water vapor was passed through the anode to produce
carbon dioxide and protons, eliminating the steam-methane reforming
and water-gas conversion reactions that occurred in conventional
hydrogen production. On the other hand, ammonia could be produced
on VN-Fe cathode with 5–14% efficiency at relatively low potentials
(0.3–0.6 V). More notably, the author proposed a concept of an elec­
trochemical HB system, as shown in Fig. 5, combining proton ceramic
membrane fuel cell with the proton conductive membrane reactor, to
achieve the purpose of using hydrogen as a by-product to recover elec­
tricity and purify the reactant nitrogen from ambient air. Energy anal­
ysis showed that the system could consume less energy and release 60%
less carbon dioxide than conventional processes under conditions of
>35% FENH3 and low applied bias (<0.6 V). The low-emission energy
cycle using ammonia as a medium is instructive, although it is only a
concept at the moment, as decentralization holds great promise in
remote areas where distribution costs are prohibitive. Similarly, Firman
et al. [67] proposed an integrated system of N2 production, NH3 syn­
thesis, and power generation, the energy efficiency of which could reach
69.3%. Therefore, an ammonia-centered energy system has demon­
strated significant potential.
B. Wang et al. Fuel Processing Technology 235 (2022) 107380

Fig. 5. Conceptual Design of the Electrochemical Haber-Bosch process [32].

3. Direct ammonia SOFC/PCFC of ammonia through polymeric membrane electrolytes leads to a

Ammonia fuel cells can be divided into external decomposition and
direct utilization according to the working gas. External decomposition
breaks down ammonia into nitrogen and hydrogen by an additional
apparatus, which adds complexity and cost to the system. In contrast,
the direct ammonia fuel cell does not require external gas reforming,
leading to simplified system and better cost-effectiveness [68]. Direct
ammonia fuel cells are divided into two major types, namely alkaline
electrolyte types (alkaline solution, molten hydroxide, alkaline mem­
brane) and solid electrolyte types. Their advantages and disadvantages
are summarized in Table 5.
The reactions between anode and cathode of alkaline direct
ammonia fuel cell are shown in Eqs. (2) & (3). Cairns et al. [69] first
developed a fuel cell directly fueled by ammonia in 1960s, using high-
concentration KOH solution as an electrolyte. The molten KOH-NaOH
is also frequently studied because of its high ionic conductivity and
efficient fuel oxidation [70]. However, hydroxide electrolyte tends to
react with carbon dioxide to form carbonate precipitates that cause
blockage and affect the long-term stability, which remains a critical
challenge. On the other hand, anion exchange membrane fuel cells,
which operate on similar working principle, demonstrate improved
tolerance over precipitation formation [71,72]. However, the crossover
decrease in open circuit voltage (OCV) and efficiency. In addition, the
kinetics of ammonia oxidation is relatively sluggish, and some inter­
mediate products may be adsorbed on the surface of noble metal,
resulting in catalyst inactivation and affecting long-term stability [71].
Another type of solid electrolyte fuel cell is suitable for directly using
ammonia gas as fuel, which has high operating temperature and power
generation efficiency.
O2 + 2H2 O + 4e− →4OH− (2)
2NH3 + 6OH− →N2 + 6H2 O + 6e− (3)
The electrolyte material could be either oxygen ion conductor
(SOFC) or proton conductor (PCFC) and such fuel cell type has displayed
some unique features: (1) the operating temperatures of SOFC/PCFC
match well with the decomposition temperature of ammonia; (2) Ni-
cermet, which is an exclusively applied material for fuel electrode,
also functions as an effective catalyst for ammonia decomposition at
temperatures above 773 K; (3) ammonia fuel has no coking problem,
which is one of the key problems associated with hydrocarbon fuels; (4)
the endothermic nature of ammonia decomposition makes thermal
management more convenient, because the cathode does not need to be
cooled by excess air, thus improving the system efficiency [6,9].

Table 5
Comparison of different direct ammonia fuel cells [7].
Electrolyte types Temperature Electrolyte transported Advantages Disadvantages
(◦ C) ions

Alkaline 25–100 OH− • Low operating temperature. • Slow oxidation at low temperatures; low power
electrolyte • No ammonia decomposition process; low density.
cost. • Degradation of membrane electrolytes.
• Ammonia crossover.
Solid electrolyte 500–1000 O2− /H+ • High power density. • Incomplete decomposition of ammonia at low
temperature.
• Catalyst deactivation and long-term stability.

8
B. Wang et al.
Therefore, SOFC/PCFC is a very suitable candidate for direct ammonia
utilization.
3.1. Working principle of direct ammonia SOFC/PCFC
Direct ammonia SOFC/PCFC is a process that converts chemical
energy into electrical energy by dividing the oxidation of ammonia in
two chambers using electrolytes that transport different ions. Generally,
the oxidation process of ammonia is divided into two stages. The
decomposition of ammonia first occurs when ammonia diffuses through
the porous anode [6], during which ammonia is converted into
hydrogen and nitrogen. The existence of nitrogen may cause a certain
dilution effect on hydrogen, and thus has a negative effect on cell per­
formance. As shown in Fig. 6, for SOFC, oxygen ions which are gener­
ated from oxygen reduction at cathode were transported to anode and
react with hydrogen, producing water and releases electrons. However,
if decomposition is not complete before reaching the electrochemical
active region (EAR), oxygen ion could react directly with remaining
ammonia via the side reaction, leading to the formation of nitrogen
oxide as an undesired side reaction. On the contrary, hydrogen first loses
electrons at the anode of PCFC to form protons, which travel through the
electrolyte to the cathode to form water with oxygen and electrons. It
can be seen that for PCFC, the anode is not involved in the oxidation of
nitrogen, so no nitrogen oxides are formed.
3.2. Development of direct ammonia SOFC/PCFC
Since the 1980s, high-temperature fuel cells using ammonia as fuel
have undergone considerable development, and the performance has
also made a huge leap. The development history of direct ammonia
SOFC/PCFC is shown in Fig. 7.
In 1980s, Vayenas et al. [73] developed YSZ-based solid electrolyte
reactor for ammonia conversion and utilization, and discovered the
generation of electric power as well as NO. Wojcik et al. [74] conducted
the first systematic study on SOFC directly fed with ammonia, during
which YSZ electrolyte support has been tested with silver/platinum
electrodes and iron catalyst. A maximum power density of 50 mW cm− 2
can be obtained at 1073 K. Since then, oxygen ion conduction SOFC has
been extensively studied with different electrodes and electrolytes, in
which the related research results are shown in Table 6. The electrolyte-
electrode system of ammonia SOFC is basically similar to that of SOEC
for ammonia synthesis, of which YSZ is the most mature and classic
electrolyte. Ma et al. [76] developed an anode-supported fuel cell using
dense thin film YSZ as electrolyte for direct conversion of ammonia fuel,
and obtained a maximum power density of 299 mW cm− 2 and 526 mW
cm− 2 at 750 ◦ C and 850 ◦ C, respectively, which was only slightly lower
than that using hydrogen as fuel. Similarly, Yang et al. [77] also used
YSZ as electrolyte, Ni-YSZ and gadolinium-doped ceria (GDC)-
Fig. 6. Principle of direct ammonia SOFC/PCFC, (a): SOFC; (b): PCFC.
9
Fuel Processing Technology 235 (2022) 107380
La0.6Sr0.4Co0.2Fe0.8O3− δ (LSCF) as anode and cathode, achieving the
power densities of 329 mW/cm2 at and 700 ◦ C. There are still a lot of
studies using YSZ today, and the power density has been greatly
improved. For example, Zhong et al. [78] introduced pyrochlore
Pr2B2O7 oxides (B– – Zr, ZrSn, Sn, PZO/PZSO/PSO) and perovskite
(B–– Ti, PTO) as cathodes in direct ammonia SOFC with YSZ electrolyte.
It was found that PZO with B-site cationic defects displays enhanced ion
and electron transport, and excellent cell performance was obtained:
1220 mW cm− 2 at 800 ◦ C and 250 mW cm− 2 at 600 ◦ C. Based on such
excellent performance, they performed ammonia SOFC experiments
again with YSZ as electrolyte, the difference is that they replaced the
cathode with Sr1+xY2-xO4+δ (SYO)-YSZ, 240 mW/cm2 and 1210 mW/
cm2 were obtained at 600 ◦ C and 800 ◦ C, and the structure showed no
significant degradation even after 100 h of continuous operation [79]. In
addition, Shy et al. [80] also tested the performance of anode supported
direct ammonia fuel cell with Ni-YSZ||YSZ|| La0.6Sr0.4CoO3 (LSC)-GDC
structure at 1 atm and 3 atm respectively, and found that both pressure
and temperature rise can increase the power density under the same
operating conditions.
Sm-doped Ceria (SDC) is also a common electrolyte, Ma et al. [81]
designed a medium temperature ammonia fuel cell with Ni-SDC anode,
an SDC (50 μm) electrolyte, and an Sm0.5Sr0.5CoO3− δ (SSC)-SDC cath­
ode, and obtained a power density of 253 mW cm− 2 at 700 ◦ C, which
was comparable to the performance of hydrogen. Meng et al. [82]
compressed the electrolyte thickness to 10 μm and replaced the cathode
with a more active Ba0.5Sr0.5Co0.8Fe0.2O3− δ (BSCF) due to the thicker
electrolyte thickness of the above cell. As a result, the power density
increased to 1190 mW cm− 2 at 700 ◦ C. In a recent study, Song et al. [83]
also designed an SDC-supported cell with
La0.52Sr0.28Ti0.94Ni0.03Co0.03O3− δ (LSTNC) as anode and
Ba0.5Sr0.5Co0.8Fe0.2O3− δ (BSCF) as cathode, and achieved a power den­
sity of 361 mW cm− 2 at 800 ◦ C. At the same time, the anode sintering
defect was improved to a certain extent, and it was operated stably for
120 h because the surface of the anode is decorated with in-situ dis­
solved and strongly coupled NiCo alloy nanoparticles. In order to be
more in line with the low temperature development direction of SOFC,
LiNi0.815Co0.15Al0.035O2 (NCAL) of semiconductor structure was used to
dope SDC, and Ni-NCAL was used as electrode material, which could
reach 501 mW cm− 2 and 755 mW cm− 2 at 500 ◦ C and 550 ◦ C, respec­
tively [84]. Other anionic electrolytes, such as La0.9Sr0.1Ga0.8Mg0.2O2.85
(LSGM) and Sc0.1Zr0.9O1.95 (SSZ), have also been used in ammonia fuel
cells, and have obtained competitive performance.
To avoid NOX poisoning at the anode, proton-conduction electrolytes
have been attempted in ammonia fuel cells because the anode of PCFC
does not involve the side reactions of NOx generation. The proton
conduction electrolyte used in ammonia PCFC is basically the same as
that used in ammonia synthesis by PCEC. Perovskite electrolyte is the
most commonly used at present, among which, BaCeO3-based materials
B. Wang et al.
Fig. 7. Development History of Direct Ammonia SOFC/PCFC [73–75,78,79,85,86,91,100].
are the most widely studied. Maffei et al. [85] developed a PCFC using
BaCe0.8Gd0.15Pr0.05O3− δ (BCGP) as electrolyte, NiO- BaCe0.85Eu0.15O3
(BCE) as anode and Pt as cathode. The results showed that the cell could
operate normally at a temperature as low as 450 ◦ C using ammonia as
the fuel, but its peak power density at 600 ◦ C is only 28 mW cm− 2.
Pelletier et al. [86] also used BaCe0.8Gd0.19Pr0.01O3− δ (BCGP) as elec­
trolyte, and its cell performance was also not high, with a peak power
density of 35 mW cm− 2 at 700 ◦ C. In contrast, Zhang et al. [87] produced
PCFC with BaCe0.8Gd0.2O3− δ (BCGO) as electrolyte, Ni-Ce0.8Gd0.2O1.9
(CGO) as anode and Ba0.5Sr0.5Co0.8Fe0.2O3− δ (BSCFO)-CGO as cathode
by dry pressing method. Open circuit voltages of 1.12 V and 1.1 V were
obtained at 600 ◦ C and 650 ◦ C respectively, and maximum power den­
sity of 147 mW cm− 2 was obtained at 600 ◦ C due to the compaction of
BCGO (no porosity) and complete decomposition of ammonia. Similarly,
Ma et al. [88] obtained better performance in PCFC on Ni-BCGO||
BCGO||La0.5Sr0.5CoO3− δ (LSCO)-BCGO structure, obtaining a maximum
power density of 355 mW cm− 2 at 700 ◦ C. Lin et al. [89] doped BaCeO3
with Zr and Y to form a BaZr0.1Ce0.7Y0.2O3− δ (BZCY) electrolyte, and
used NiO-BZCY as the anode and Ba0.5Sr0.5Co0.8Fe0.2O3− δ (BSCF) as the
cathode to achieve a maximum power density of 390 mW cm− 2 at
750 ◦ C. In contrast, the performance of PCEC with BZCY as electrolyte
was greatly improved by Aoki et al. [90]. The anode and cathode used
were Pd and La0.6Sr0.4Co0.2Fe0.8O3–δ (LSCF), respectively, and a power
density of 580 mW cm− 2 could be obtained at 600 ◦ C. They attributed
this high performance to the fact that the ohmic contact of the BZCY/Pd
junction allows a large number of protons to be accommodated in the
interfacial region, thus promoting the incorporation of protons from Pd
into BZCY according to the hole-proton thermodynamic equilibrium,
accelerating the anodic charge transfer reaction. Although the perfor­
mance of PCFC is generally inferior to SOFC, its performance has made
great progress after years of development, and the largest power density
of tubular cell reported so far comes from Pan et al. [91]. They prepared
the anode supporting substrate Ni-BaZr0.1Ce0.7Y0.1Yb0.1 (BZCYYb) by
phase-inversion method, and then attached the electrolyte layer BZCYYb
and the cathode layer PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF) to it. A power
density of 1.078 W cm− 2 was obtained at 700 ◦ C. In addition, they added
a catalytic Fe layer on the anode side, which greatly improved the
durability of the cell because it facilitated ammonia decomposition and
functioned as the protection layer of Ni anode. The phase-inversion
process will form pores inside the material that are conducive to gas
transport because of the different degrees of shrinkage in different di­
rections. The structure has great research value and is worthy of further
10
Fuel Processing Technology 235 (2022) 107380
exploration. by researchers Recently, Shao’s group doped Pd and Ni into
BZCYYb, which considerably enhances the proton conductivity, anode
electrocatalytic activity, and charge transfer at the anode-electrolyte
interface [92,93].
The anodes of direct ammonia SOFC/PCFC involve decomposition
and oxidation of ammonia, so the function of the anodic material largely
determines the performance of the cell. Similar to PCEC ammonia, noble
metals are initially used for anodes. At present, the most commonly used
anodes in SOFC/PCFC are composite anodes composed of single metal
and conductive ceramic materials, among which Ni-YSZ is the most
classical, and most of the SOFC/PCFC studies using ammonia gas as fuel
also adopt it. The reason is that Ni-YSZ has good catalytic activity for
ammonia decomposition at high temperature, which is higher than Ni/
Al2O3, Ni/CeO2, Ni/Sm2O3, Ni/Gd2O3 and other materials [94]. In
addition, doped CeO2 ceramics are also an anode material that has been
extensively studied, including SDC, GDC, CGO, etc. It has excellent
mixed ion electron conductivity and high catalytic activity for ammonia
decomposition. Ni and perovskite structure proton conduction oxide
composite is also a hot anode material in recent years. The choice of
cathode material is also a major factor in determining cell performance
as cathode activation polarization plays a dominant role at lower tem­
peratures [95]. LSCF and LSM are considered as the most suitable
cathode materials for their good thermal compatibility with electrolytes
and high conductivity. Perovskites, double perovskite and ruddlesden-
popper (RP) structures are also the most commonly used cathode ma­
terials. The cathode of direct ammonia fuel cell is exactly the same as
other SOFCs, and the relevant summaries have been described in detail
in other reviews [9].
3.3. Thermodynamics and kinetics of ammonia decomposition
As mentioned above, the reaction of ammonia SOFC/PCFC at the
anode is widely accepted as a two-step reaction. The performance of
ammonia SOFC/PCFC will be similar to that of hydrogen SOFC/PCFC if
ammonia can be rapidly decomposed into hydrogen and nitrogen, so the
ammonia decomposition rate will have a decisive influence on the
performance of SOFC/PCFC. The ammonia decomposition rate depends
on multiple factors, such as the partial pressure, flow rate, operating
temperatures and anode materials [9,96,101]. Aside form gases
involved in ammonia decomposition, water vapor could improve the
proton conductivity of electrolyte and the catalytic activity of anode
[103]. However, most cermet anodes have strong water absorption,
B. Wang et al. Fuel Processing Technology 235 (2022) 107380

Table 6
Summary of direct ammonia SOFC/PCFC.
Type Electrolyte Electrode (anode//cathode) Temperature (◦ C) Peak power density (mW/cm2) Ref.

SOFC/Anode support YSZ Ni-YSZ//SYO (0.1)-60YSZ 600 240 [79]-2022

800 1210
SOFC/Anode support YSZ NiO-YSZ//PZO 800 1220 [78]-2022
SOFC/Anode support YSZ Ni-YSZ// 800 (1 atm) 1078 [80]-2018
LSC-GDC 850 (1 atm) 1174
800 (3 atm) 1148
850 (3 atm) 1202
SOFC/Anode support YSZ Ni-YSZ//GDC-LSCF 700 325 [77]-2015
SOFC/Anode support YSZ Ni-YSZ//LSM-YSZ 900 88 [96]-2009
SOFC/Anode support YSZ NiO-YSZ//LSM-YSZ 850 526 [76]-2007
SOFC/Anode support YSZ Ni-YSZ//LSM-YSZ 800 200 [97]-2007
SOFC/Anode support SDC/NCAL Ni-NCAL//Ni-NCAL 550 755 [84]-2022
SOFC/Electrolyte support SDC LSTNC-SDC//BSCF 800 361 [83]-2020
LSTN-SDC//BSCF 800 161
LSTC-SDC//BSCF 800 98
Ni-SDC//BSCF 800 314
SOFC/Anode support SDC Ni-SDC//BSCF 650 1190 [82]-2007
SOFC/Anode support SDC Ni-SDC//SSC-SDC 700 253 [81]-2006
SOFC/Electrolyte support LSGM Ni (97.5) Mo (2.5)-SDC//SSC 900 416 [98]-2015
Ni (97) Ta (3)-SDC//SSC 900 322
Ni (97) W (3)-SDC//SSC 900 313
SOFC/Electrolyte support LSGM Ni-SDC//Pt 900 120 [99]-2014
Fe-SDC//Pt 900 242
Co-SDC//Pt 900 85
Ni (40) Fe (60)-SDC//SSC 900 360
Ni-SDC//SSC 900 253
SOFC/Anode support SSZ Ni-YSZ/Ni-SSZ//LSM-SSZ 800 1028 [100]-2012
Ni (97.5) Fe (2.5)-YSZ/Ni-SSZ//LSM-SSZ 800 1150
PCFC/Anode support BCY10 Ni-BCY25//SSC 650 216 [101]-2015
PCFC/Anode support BZCY Pd//LSCF 600 580 [90]-2017
PCFC/Anode support BZCY NiO-BZCY//BSCF 750 390 [89]-2010
PCFC/Anode support BCGP1 NiO-BCE//Pt 600 28 [85]-2008
PCFC/Electrolyte support BCG Pt//Pt 700 25 [86]-2005
BCGP2 Pt//Pt 700 35
PCFC/Anode support BCGO Ni-CGO//BSCFO-CGO 600 147 [87]-2008
PCFC/Anode support BCGO Ni-BCGO//LSCO-BCGO 700 355 [88]-2006
PCFC/Anode support BCNO NiO-BCNO//LSCO 700 315 [102]-2007
PCFC/Anode support BZCYYb Ni-BZCYYb//BCCY 650 383 [93]-2022
BZCYYbN Ni-BZCYYbN//BCCY 650 523
PCFC/Anode support BZCYYb Ni-BZCYYb//PBSCF 700 1078 [91]-2022
PCFC/Anode support BZCYYb Ni-BZCYYb//BCFZY 650 450 [92]-2021
Ni-BZCYYbPd//BCFZY 650 600
BZCYYbPd Ni-BZCYYbPd//BCFZY 650 724

Note: YSZ: Yttria Stabilized Zirconia; SYO (0.1): Sr1+xY2-xO4+δ (x = 0.10); PZO: Pr2Zr2O7; LSC: La0.6Sr0.4CoO3; GDC: Gd-doped Ceria; LSCF: La0.6Sr0.4Co0.2Fe0.8O3–δ;
LSM: La1− xSrxMnO3; SDC: Sm-Doped Ceria; NCAL: LiNi0.815Co0.15Al0.35O2; LSTNC: La0.52Sr0.28Ti0.94Ni0.03Co0.03O3− δ; LSTN: La0.52Sr0.28Ti0.94Ni0.06O3− δ; LSTC:
La0.52Sr0.28Ti0.94Ni0.06O3− δ; BSCF: Ba0.5Sr0.5Co0.8Fe0.2O3− δ; SSC: Sm0.5Sr0.5CoO3− δ; LSGM: La0.9Sr0.1Ga0.8Mg0.2O2.85; SSZ: Sc0.1Zr0.9O1.95; LSM: La1− xSrxMnO3; BCY10:
BaCe0.90Y0.10O3− δ; BCY25: BaCe0.75Y0.25O3− δ; BZCY: BaZr0.1Ce0.7Y0.2O3− δ; BCGP1: BaCe0.8Gd0.15Pr0.05O3− δ; BCE: BaCe0.85Eu0.15O3; BCG: BaCe0.8Gd0.2O3-δ; BCGP2:
BaCe0.8Gd0.19Pr0.01O3− δ; BCGO: BaCe0.8Gd0.2O3− δ; CGO: Ce0.8Gd0.2O1.9; BSCFO: Ba0.5Sr0.5Co0.8Fe0.2O3− δ; LSCO: La0.5Sr0.5CoO3− δ; BCNO: BaCe0.9Nd0.1O3− δ; BZCYYb:
BaZr0.1Ce0.7Y0.1Yb0.1; BCCY: BaCo0.7Ce0.24Y0.06O3− δ; BZCYYbN: Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.95Ni0.05O3− δ; PBSCF: PrBa0.5Sr0.5Co1.5Fe0.5O5+δ; BZCYYbPd: Ba
(Zr0.1Ce0.7Y0.1Yb0.1)0.95Pd0.05O3− δ; BCFZY: BaCo0.4Fe0.4Zr0.1Y0.1O3− δ.

resulting in the active site being occupied, thus affecting ammonia
decomposition. Yang et al. [101] studied the decomposition character­
istics of ammonia on Ni-BaCe0.75Y0.25O3− δ (BCY25), and the results
showed that mixing 0.8% water vapor in the ammonia would cause the
ammonia conversion rate to plunge from 98.6% to 55%. Therefore, the
influence of water vapor partial pressure on ammonia decomposition
and cell performance is not linear, which requires special optimization.
Ammonia conversion rate generally presents a trend of decrease with the
increase of fuel flow rate [9,104]. For power density, there are two
opposite trends. More hydrogen will be provided with the increase of
fuel when the fuel flow rate is low, thus increasing the power density.
However, the decomposed hydrogen will be taken away by the excessive
flow rate when the fuel flow rate increases to a certain amount, resulting
in a decrease in power density [9]. The decomposition of ammonia is a
temperature-dependent reaction, and fortunately, ammonia decompo­
sition can be performed very well at SOFC/PCFC operating tempera­
tures. Generally speaking, the complete decomposition of ammonia can
be achieved at a temperature of 600–800 ◦ C with the presence of anodic
catalyst [81,105]. The above thermodynamic factors have been
comprehensively summarized by Xu et al.in a previous review [9].
Ammonia decomposition is also a highly catalyst-dependent reac­
tion. Anode materials are generally divided into catalytic part and car­
rier part. The catalytic part is generally composed of metal material, and
is responsible for catalytic ammonia decomposition and hydrogen
oxidation. At present, noble metals, non-noble metals, bimetals, transi­
tion metal carbides and nitrides have been reported. Ganley et al. [106]
reported the performance of loading various metals on alumina carrier
for ammonia decomposition, and the results showed that the order of
catalytic effect was: Ru > Ni > Rh > Co > Ir > Fe > Pt > Cr > Pd > Cu.
Ru is the metal with the highest catalytic activity of ammonia decom­
position reported at present. The ammonia decomposition rate could
reach 99% when Choudhary and Goodman used 10% Ru/SiO2 at 650 ◦ C
[107]. However, Ru is a noble metal, leading to great cost obstacles for
commercialization. Ni is a relatively cheap metal, and its ammonia
decomposition ability is second only to Ru due to its suitable nitrogen
binding energy. Therefore, Ni is the most commonly used anodic cata­
lytic layer for ammonia SOFC/PCFC. The nitrogen binding energy of the
catalyst is the main factor determining the catalytic effect. Too strong

11
B. Wang et al.
nitrogen binding energy will lead to the poisoning of the active site
although the ammonia molecule is first adsorbed on the surface of the
active metal particle. Therefore, the nitrogen binding energy of the
anode catalyst needs to be adjusted to an appropriate range. It has been
reported that the optimal nitrogen binding energy range of catalysts for
ammonia decomposition is 544–586 kJ mol− 1 [108,109]. The nitrogen
binding energy of Ni can be adjusted by adding multiple metallic center.
Hashinokuchi et al. [110] introduced Cr into Ni/SDC anode to enhance
the ammonia SOFC performance, and found that the synergistic effect
between Cr and Ni could not only enhance the reforming of ammonia,
but also enhance the cell stability. The peak power density of Cr-Ni/SDC
anode was higher than that of Ni/SDC anode alone (345 mW cm− 2 vs
258 mW cm− 2 at 700 ◦ C). Besides, they found that the introduction of
Mo can also improve the performance of ammonia SOFC with Ni/SDC
anodes.
It is worth noting that in addition to the catalytic properties of the
metallic center, the microstructure of the catalyst and the carrier also
have an influence on the activity of ammonia decomposition by affecting
the configuration of the active site. As shown in Fig. 8, Zhang et al. [111]
used an alumina carrier to study the influence of Ni nanoparticle size on
ammonia decomposition and pointed out that the microcrystalline size
of Ni particles was the main factor, and the catalytic activity of Ni
particles was the highest at 1.8–2.9 nm. This may be because the
ammonia decomposition reaction is very sensitive to a plane of the Ni
single crystal. The loading mode of catalyst will have an impact on the
microstructure of the anode. In previous studies by Zhang et al. [112], Ni
ions loaded onto the carrier by coprecipitation and adsorption showed
higher catalytic activity compared with the traditional impregnation
method. Molouk et al. [113] also found that the catalytic activity of Ni-
GDC prepared by physical mixing method and nitroglycine method was
different, among which nitroglycine method prepared catalyst with
higher specific surface area. Besides, the synthesis parameters used in
different loading modes also deeply affect the structural characteristics
of the prepared catalysts. When Ni particles are loaded onto silica car­
riers by precipitation method, the synthesis time will affect the types of
Ni2+ particles deposited, and too long time will lead to the formation of
polysilicates, thus reducing porosity [114]. The amount of catalyst can
affect not only the particle size but also the phase structure. Itagaki et al.
[115] used Ni-SDC with different Ni loadings as anodes of ammonia
SOFC to explore the effect of the load. The results showed that the best
effect could be achieved with 10 wt% Ni loadings, and complete con­
version of ammonia could be achieved at 608 ◦ C. But when the loading
Fig. 8. Effect of Ni0 particle size on the forward NH3 turnover rate (TOFNH3)
for NH3 decomposition. Solids: Ni/Al2O3; hollows: Ni/La-Al2O3. Conditions:
5.0 mg catalyst, dp = 100–150 μm, dilution ratio = 1:100, total space velocity
= 6,000,000 mlgcat− 1 h− 1, 15 kPa NH3, balance He [111].
12
Fuel Processing Technology 235 (2022) 107380
was increased to 40–50 wt%, the catalytic decomposition effect
decreased, which might be because excessive Ni particles would produce
agglomeration and reduce the specific surface area. For the power
density, the effect of 10 wt% and 40 wt% loading was similar, because
the increase of Ni increased the electronic conductivity of the anode, and
thus the oxidation reaction of the anode was enhanced.
The carrier of the anode is usually an ion or proton conductor used as
an electrolyte. The same catalyst supported on different carriers will
present different active sites. Nakamura et al. [116] explored the Ni’s
catalytic effect on ammonia decomposition using different carriers, and
among Y2O3, CeO2, MgO, La2O3, Al2O3, and ZrO2, Ni/Y2O3 had the
highest catalytic activity. It is believed that different carriers change the
electronic states of Ni, thus affecting the binding energy of N-Ni. On the
other hand, the basicity of the carrier is considered to be an major factor
affecting the catalytic ammonia decomposition ability, and higher sur­
face basicity is conducive to ammonia adsorption and nitrogen desorp­
tion. Yang et al. [101] compared the effects of Ni/BCY25, Ni/GDC and
Ni/YSZ as direct ammonia SOFC anodes, and Ni/BCY25 showed higher
catalytic capacity of ammonia decomposition in the temperature range
tested (350–750 ◦ C). It is believed that the proton conduction carrier has
higher catalytic activity than the ion conduction carrier, because higher
surface alkalinity and resistance to hydrogen poisoning. Okura et al.
[117] found that similar conclusions are also applicable to perovskite-
type carriers. The ammonia decomposition rate increases when the ba­
sicity of perovskite carriers increases.
3.4. Long-term durability problems
Long-term stability has been a major obstacle to the adoption of
SOFC/PCFC, and direct ammonia SOFC/PCFC is no exception. At pre­
sent, most long-term stability tests of ammonia SOFC/PCFC are based on
Ni-YSZ anodes. For example, Wang et al. [118] found that the perfor­
mance of a flat tubular cell using ammonia feed with a structure of Ni-
YSZ||YSZ||LSCF-YSZ decreased by 1.32% after 50 h of operation at
750 ◦ C and 200 mA cm− 2. Similarly, Zhang et al. [97] also used Ni-YSZ
anode to test the stability of ammonia SOFC, and the open-circuit
voltage loss was 4% after running at 800 ◦ C for >100 h. Hagen et al.
[119] tested the stability for a longer time in anode-supported planar
cell with the cell structure of Ni-YSZ||YSZ||LSM-YSZ, which was tested
for 1500 h at 850 ◦ C, 1 A cm− 2. It was found that the observed power
output decreased at a large rate during the first few hundred hours, then
leveled off at 1000 h and beyond, with degradation rates of 2–4% per
1000 h. Studies of longer dwelling time have been reported so far, which
is of great importance if ammonia SOFC/PCFCs are to be commercial­
ized. For the stack level ammonia SOFC, the long-term operation ca­
pacity of the connector, separator, collector and other corresponding
materials also needs to be addressed in addition to the single cell.
Okanishi et al. [120] tested the stability of direct feed and external
pyrolysis feed ammonia SOFC (NiO/YSZ-ZrO2-based material-
perovskite-type oxide material) in a stack of >200 W, as shown in Fig. 9.
Although the voltage of the direct ammonia system decreased slightly
with the operation time, its stability was almost comparable to that of H2
fuel system. More importantly, SOFC fuelled directly by ammonia
maintained power above 200 W without significant degradation. The
test of kilowatt stack was carried out by Kishimoto et al. [105], who
integrated 30 single cells with Ni/YSZ-ZrO2-based material-LaNiO-
based perovskite material structure. As can be seen from Fig. 10, the
maximum power density of direct ammonia and hydrogen/nitrogen
both reached the kilowatt level. A small decrease in average voltage was
observed at the beginning of the 1000 h stability test of the direct
ammonia feed, followed by a gradual recovery during the first 200 h
before the voltage became almost stable. As a result, the direct ammonia
SOFC has the potential to run for a long time, as seen in stability tests of
single cells and stacks.
At present, the widely recognized factor affecting the stability of
direct ammonia SOFC/PCFC is the nitriding of Ni at the anode, which
B. Wang et al. Fuel Processing Technology 235 (2022) 107380

Fig. 9. (a) I-V and I-P characteristics of the SOFC stack (consisted of 10 anode-supported planar cells with 95 cm2 of active area developed by Noritake Co. Ltd.) at
770 ◦ C. Anode gas: 75% H2–25% N2 (black line), NH3 (red line), decomposed NH3 (green line), and autothermally cracked NH3 (blue line); Cathode gas: air. (b): Time
course of the voltage and power at 770 ◦ C for the direct NH3-fueled (red line) and H2-fueled (black dotted line) SOFC stacks. The current was kept at 30 and 35 A for
the NH3-fueled and the H2-fueled ones, respectively [120].

Fig. 10. (a): I-V and I-P characteristics

of the stack (consisted of 30 anode-
supported planar cells with a diameter
of 120 mm and an active area of 95 cm2
fabricated by Noritake Co., Ltd.) with
direct ammonia fuel (FNH3 = 8.19 L
min− 1, FAir = 50 L min− 1) and hydro­
gen‑nitrogen mixture fuel (FH2 = 12.3 L
min− 1, FN2 = 6.14 L min− 1, FAir = 50 L
min− 1). (b): Average cell voltage during
1000 h durability test with a stack
fueled with the direct ammonia and
with that fueled with the externally
decomposed ammonia [105].

Fig. 11. SEM images of Ni/YSZ cermet anode surface. (a) as-reduced in 15% H2-85% Ar and (b, c) fueled with 66.7% NH3-1.7% H2O-31.6% N2 at (b) 700 ◦ C or (c)
600 ◦ C for 24 h. (d) EDX spectra at the spots marked with a star in (a)–(c) [77].

13
B. Wang et al.
will cause changes in the microstructure of the anode, and then affect
the normal working ability of the anode [6,7,9]. The excess ammonia
reacts with Ni via Eq. (4) to form Ni3N when the catalyst at the anode is
not strong enough to decompose ammonia completely. Ni3N in a
reducing atmosphere or at higher temperatures will undergo decom­
position of Eqs. (5) & (6) to regenerate Ni particles again. Yang et al.
[77] tested SEM images of Ni/YSZ powder before and after ammonia
treatment at 600 ◦ C and 700 ◦ C, as shown in Fig. 11. Fig. 11 (a) showed
Ni/YSZ without ammonia treatment, which was composed of many
small grains and had a smooth surface. The Surface of Ni became rough
and there were many micropores smaller than 100 nm after 700 ◦ C
treatment, as shown in Fig. 11 (b). Some studies believe that these mi­
cropores increase the specific surface area of the anode catalyst, which is
conducive to the decomposition of ammonia to a certain extent.
Furthermore, the surface of Ni treated at 600 ◦ C was rougher and
bonded, indicating that the nitride was more serious. Further analysis by
EDX showed that the surface nitrogen of Ni/YSZ was higher after 600 ◦ C
treatment. XRD results showed that Ni3N peaks exist in the Ni/YSZ
treated at 600 ◦ C, indicating that the Ni/YSZ is a stable phase at 600 ◦ C.
Besides, the coarsening of Ni particles is also considered as one of the
factors affecting cell stability, and the catalytic ammonia decomposition
ability of Ni particles has the corresponding optimal particle size [104].
6Ni + 2NH3 →2Ni3 N + 3H2 (4)
2Ni3 N + 3H2 →6Ni + 2NH3 (5)
2Ni3 N→6Ni + 2N2 (6)
The nitriding of Ni in the anode is affected by many factors, such as
temperature and fuel composition. As mentioned above, the catalytic
activity of the Ni-based anode will be greatly improved with the increase
of temperature, thus the amount of undecomposed ammonia will be
reduced, and the nitriding reaction of Ni will be correspondingly
weakened. At the same time, Ni3N cannot exist stably in high temper­
ature above 600 ◦ C. Therefore, high temperature operation can improve
the stability of ammonia SOFC/PCFC. Stoeckl et al. [121] tested the
stability of a stack composed of ten Ni-GDC||scandia-stabilized zirconia
(ScSZ)||LSM-ScSZ chip cells at 835 ◦ C and 0.226 A cm− 2, the
Fig. 12. Above: time courses of OCV of anode supported cell fueled with 60.0% H2–1.0% H2O-39.0% N2 and 66.7% NH3–1.7% H2O-31.6% N2 during thermal cycling
tests; cathode gas: O2. Below: Illustration of the anode supported cell after the temperature cycling test in NH3 [77].
14
Fuel Processing Technology 235 (2022) 107380
degradation rate is only 1.1% kH− 1. However, high temperature oper­
ation is not in line with the development direction of low temperature in
SOFC/PCFC, and high temperature will also bring many problems such
as thermal matching of materials, sealing, nitriding of other parts and so
on. Although the stack tested by Stoeckl et al. have good stability,
nitridation was found in accessories such as Cr connectors and Ni con­
tact nets [121]. Similarly, Kishimoto et al. [105] conducted tests in Ni-
YSZ anode-supported stacks for up to 1000 h and found that the anode
structure remained intact, but the metal cell separator on the anode side
was nitrided. Notably, dynamic operation of temperature is often
required in practical operation, but frequent changes in temperature are
devastating to the damage of the anode structure. Yang et al. [77] per­
formed the stability test of the Ni/YSZ cermet anode supported coin cell
reciprocatingly between 600 ◦ C and 700 ◦ C. As shown in Fig. 12, as the
temperature was changed back and forth, there was an irreversible loss
of OCV in the ammonia-fed cell, while the hydrogen-fed was unaffected.
The reason was that Ni was nitrided at low temperature, and decom­
posed again at high temperature. Repeated reciprocation would cause
changes in volume and stress, which eventually led to the cracking of the
Ni-YSZ support layer and reduced cell performance. Fuel flow is another
key factor affecting Ni nitridation. We all know that if ammonia can be
quickly decomposed after reaching the anode, it will approach the
performance of hydrogen SOFC/PCFC. Similarly, after ammonia is
decomposed quickly, there will be no excess ammonia that can react
with Ni, thereby improving the stability of the cell [9].
Based on the above analysis, the core of improving the stability is to
minimize the chance of ammonia and Ni contact. First, as mentioned
above, raising the temperature and lowering the ammonia fuel flow is
the easiest way to improve stability. However, these two methods are
not conducive to the large-scale application of ammonia SOFC/PCFC
because of the problems of connection and sealing caused by high
temperature and the reduction of power density caused by low flow rate.
Using an external ammonia cracker seems to be another way to improve
stability [105,120], so that the ammonia content in the fuel entering the
anode is greatly reduced, thus avoiding Ni nitridation. But doing so will
undoubtedly add additional costs, thus requiring a more comprehensive
economic assessment.
The introduction of the second active component into the Ni catalyst
B. Wang et al.
can not only improve the ammonia catalytic decomposition ability, but
also inhibit the agglomeration and nitridation of Ni particles. Hashino­
kuchi et al. [110] introduced Cr in the Ni-SDC anode as second active
metal, using La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM) as the electrolyte and
Sm0.5Sr0.5CoO3-δ (SSC) as the cathode. As shown in Fig. 13, they
measured the peak power densities of Ni97-Cr3 and Ni/SDC cells after
NH3 exposure under open circuit conditions at 873 K for 30 h. Among
them, the performance of Ni/SDC decreased by nearly 20% after 30 h,
while the decrease of Ni97-Cr3 was only 4%, and this only appeared in
the first 10 h and remained basically unchanged after that, indicating
that the addition of Cr greatly improved the stability performance of Ni.
The reason may be that Cr will form CrN particles in the atmosphere of
ammonia, and its surface free energy is low, which can inhibit the
agglomeration of Ni. CrN can not only enhance the wettability of Ni
particles by anchoring them to the interface, but also reduce the direct
contact of adjacent expanded Ni particles. Similarly, Wang et al. [118]
also expressed similar conclusions. Adding Ba to the anode of flat-tube
cells with Ni-YSZ could reduce the degradation rate of cell from
1.32% to 0.47%. To sum up, long-term stability of direct ammonia
SOFC/PCFC is one of its biggest limitations compared to hydrogen fuel.
Unfortunately, there are few studies related to the long-term operation
test, and there has been scarce attempt to improve long-term stability,
which is a critical property required for large-scale commercialization.
Therefore, the related research needs further research attention.
4. Challenges and recommendations
The previous section has fully discussed the principles, advantages
and disadvantages, and the latest developments of SOEC/PCEC elec­
trochemical ammonia synthesis and direct ammonia SOFC and PCFC. In
the process of continuing joint development, many challenges will
inevitably be faced, so it is necessary to discuss the challenges and
possible research directions. SOEC/PCEC electrochemical ammonia
synthesis is still in the early stage of research and development. There
are still bottlenecks in the following aspects that need to be broken
through in order to fully realize its potential. The material system of
electrolyte-electrode-catalyst needs to be further improved. To further
increase the rate of ammonia production to meet industrial demands,
electrolytes need to have higher ionic/proton conductivity at low tem­
peratures, electrodes and electrocatalysts need to have higher electronic
conductivity, catalytic activity for ammonia synthesis, and the ability to
suppress competing hydrogen evolution reactions, and the physical and
chemical compatibility between these materials must also be consid­
ered. For better design of material systems, the mechanism of electro­
chemical nitrogen reduction reaction should be more studied. Some of
the current research on reaction mechanisms are more based on simu­
lation methods, but lack corresponding experimental verification [20].
More in-situ characterization methods, such as in situ X-ray diffraction
Fig. 13. Variations of maximum power densities of the Ni97-Cr3 and Ni/SDC
cells as a function of NH3 exposure time under the open-circuit conditions at
873 K [110].
15
Fuel Processing Technology 235 (2022) 107380
(in situ XRD), in situ transmission/scanning electron microscopy (in situ
TEM/SEM), in situ Raman spectroscopy (in situ Raman), etc., should be
used in the study. In addition, the mass transfer capacity can be
improved by modifying the cell/electrolyzer configuration. For
example, the multi-channel micro-honeycomb structure hydrogen fuel
cell used in the recent R-SOC study could reach 1.62 W/cm− 2 at 800 ◦ C
[122]. So the similar advanced structure can also be used for electro­
chemical ammonia synthesis. A large number of experimental results are
unreliable and difficult to replicate due to low ammonia yield and
inconsistent test methods. Therefore, in order to better develop elec­
trochemical ammonia synthesis technology, more scholars are required
to formulate complete standard protocols for researchers to use [123].
More importantly, there are too few studies on the system integration of
SOEC/PCEC electrochemical ammonia synthesis. System integration
research should use thermodynamic analysis [124], kinetic analysis,
material balance analysis, energy balance analysis and other means to
comprehensively evaluate the overall energy efficiency [125], the
impact on the environment, and product optimization of the proposed
system [126]. More system integration studies are essential before the
real realization of industrialization substitution in the future, it can also
provide an exact direction for basic research. For SOEC/PCEC electro­
chemical ammonia synthesis, there are few reviews on industrial-scale
applications, which is normal in the early stages of development. The
current ammonia production rate range is only 10− 13–10− 9 mol s− 1
cm− 2, which is far from sufficient for industrial applications. If a current
density of 0.25–0.5 A cm− 2 can be achieved with a current efficiency or
hydrogen conversion rate of 50%, then the ammonia production rate
will reach 10− 7 mol s− 1 cm− 2 [16], which can basically meet the in­
dustrial requirements. However, it is encouraging that it can be com­
bined with renewable energy, and the feature of providing waste heat
for power plants is a significant advantage, and as long as the problems
of materials and catalysts are solved, commercial development can be on
the right track.
Direct ammonia SOFC and PCFC also require further refinement of
material systems and in-depth application of advanced configurations
because they operate reversibly with the above-mentioned electro­
chemical ammonia synthesis process. At present, the decomposition of
ammonia is more dependent on high temperature and catalysis, and it is
critical to find an electrocatalyst with strong decomposition ability of
ammonia at low temperature. Yet more studies need to be conducted to
tackle the stability issue caused by nitridation of Ni-cermet anode and
thermal stress. For direct ammonia SOFC/PCFC, it is essentially the in-
situ decomposition of ammonia coupled with hydrogen SOFC/PCFC.
Therefore, as long as a catalyst can be designed that can promote the
rapid decomposition of ammonia at operating temperature and does not
produce other harmful reactions, it can be used in the same commercial
application as hydrogen fuel cells. For example, Japan had developed
kW-class ammonia fuel cells as of 2020. Denmark’s Skovgaard Invest,
Vestas, Topsoe and other companies also jointly carried out SOEC to
prepare green ammonia, and then use ammonia as SOFC’s fuel to
explore related applications, which are expected to reach MW-level
applications. On the whole, the use of ammonia as a medium for en­
ergy storage using R-SOC technology is a potential technology, and more
pilot operations are necessary.
5. Conclusions
Over the past decade, there has seen large numbers of ammonia-
related studies, which contribute to the promotion of ammonia as an
ideal carbon-free energy carrier. Ammonia synthesis and utilization via
electrochemical routes have exhibited considerable superiority over
conventional approaches such as Haber-Bosch process, in which
reversible solid oxide cells (R-SOCs) have become the vital bridging
technology that integrates the clean renewable sources and efficient
energy storage. In terms of ammonia synthesis, the electrochemical
route has enabled the employment of mild conditions without
B. Wang et al.
pressurization. Proton ceramic electrolytic cells (PCECs), in particular,
as demonstrated satisfactory production rates even at intermediate
temperature range between 500 and 600 ◦ C. With further development
of proton-conducting material and catalysts for ammonia synthesis, the
‘electrochemical Haber-Bosch Process’ is expected to be more compet­
itive due to its unique capability to be integrated with renewable energy
sources. On the other hand, ceramic fuel cells (both SOFC and PCFC)
have been exploited for direct ammonia utilization since the high
operating temperature (>600 ◦ C) could help realize in-situ ammonia
decomposition with the presence of catalysts. Some latest work even
reported performances that are comparable with hydrogen-fueled
counterpart.
In summary, production of ‘green ammonia’ via electrochemical
routes, coupled with efficient energy generation using direct ammonia
fuel cells, offers a pathway with great potential to achieve carbon
neutrality by 2050. There are significant research opportunities remain
in terms of material development including electrode/electrolyte ma­
terials and catalysts, optimization of geometric design and morphology,
and improvement of R-SOCs’ lifetime.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This research was supported by the Natural Science Foundation of
Jiangsu Province (Grant No. BK20210252) and Fundamental Research
Funds for the Central Universities (Grant No. buctrc202115).
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Bin Wang received his B.S. degree (2018) and M.S. degree
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119–123. (2021) in ‘Power Engineering and Engineering Thermophysics’
at Zhengzhou University and Jiangsu University, respectively.
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stability by Cr addition at Ni/Sm-doped CeO2 cermet anodes in NH3-fueled solid preparation of functional membranes for energy applications in
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Comparative study on ammonia oxidation over Ni-based cermet anodes for solid Chemical Engineering from Imperial College London. Now, he
oxide fuel cells, J. Power Sources 305 (2016) 72–79. is a professor at the School of Energy and Environment,
[114] H. Liu, H. Wang, J. Shen, Y. Sun, Z. Liu, Preparation, characterization and Southeast University, China. His current research is focused on
activities of the nano-sized Ni/SBA-15 catalyst for producing COx-free hydrogen the design and preparation of functional membranes for energy
from ammonia, Appl. Catal. A Gen. 337 (2008) 138–147. applications in fuel cells and membrane reactors.
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direct ammonia solid oxide fuel cells, J. Electrochem. Soc. 167 (2020), 064501. Rui Xiao is currently the dean of the School of Energy and
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alternative hydrogen carriers, Int. J. Hydrog. Energy 44 (2019) 18382–18392. Thermal Conversion and Control, Ministry of Education at
[120] T. Okanishi, K. Okura, A. Srifa, H. Muroyama, T. Matsui, M. Kishimoto, M. Saito, Southeast University. He is the distinguished professor of the
H. Iwai, H. Yoshida, M. Saito, T. Koide, H. Iwai, S. Suzuki, Y. Takahashi, Cheung Kong Scholars Program, the standing director of the
T. Horiuchi, H. Yamasaki, S. Matsumoto, S. Yumoto, H. Kubo, J. Kawahara, Biomass Energy Committee of Renewable Energy Society, and
A. Okabe, Y. Kikkawa, T. Isomura, K. Eguchi, Comparative study of ammonia- the member of the Chinese Society of Engineering Thermo­
fueled solid oxide fuel cell systems, Fuel Cells 17 (2017) 383–390. physics. He received his Ph.D. degree (2005) and M.S. degree
[121] B. Stoeckl, M. Preininger, V. Subotić, S. Megel, C. Folgner, C. Hochenauer, (1997) in “Thermal Engineering” at Southeast University. He
Towards a wastewater energy recovery system: the utilization of humidified served as a visiting scientist at University of Kentucky
ammonia by a solid oxide fuel cell stack, J. Power Sources 450 (2020), 227608. (2007–2008) and University of Cambridge (2014). His research
[122] M.F. Rabuni, N. Vatcharasuwan, T. Li, K. Li, High performance micro-monolithic expertise is in the clean utilization of coal and biomass, CO2
reversible solid oxide electrochemical reactor, J. Power Sources 458 (2020), capture, and bio-fuels.
228026.
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ammonia synthesis, J. Energy Chem. 61 (2021) 149–154.

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