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OLIVIER GUILLON (Orcid ID : 0000-0003-4831-5725)
Article type : Review Article
Ceramic materials for energy conversion and storage: A perspective
Olivier Guillon1,2,3
1Institute of Energy and Climate Research: Materials Synthesis and Processing (IEK-1),
Forschungszentrum Jülich GmbH
52425 Jülich, Germany
2Jülich Aachen Research Alliance JARA-Energy, 52425 Jülich
3Institute of Mineral Engineering,
RWTH Aachen University,
Germany
Abstract
Advanced ceramic materials with tailored properties are at the core of established and emerging
energy technologies. Applications encompass high-temperature power generation, energy
harvesting and electrochemical conversion and storage. New opportunities for materials design,
the importance of processing and material integration and the need for long-term testing under
realistic conditions are highlighted in the present perspective.
Introduction
If you ask non-specialists about the role of ceramics in energy conversion and storage, you might
get the following type of answer: “Really? I don’t know… But ceramics are yet brittle!”. For most
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users, system engineers and operators, customers in a broad sense, what matters is that devices
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work properly and meet the specifications and expectations. What is “inside”, i.e. which
materials have been developed and used for the application, is at this level not relevant. And
even if ceramic materials are essential for a given technology, they are in most of the cases not
visible because of the housing necessary for safe operation. That’s why the role of ceramics-
although offering unique functionalities - is in general largely underestimated. Furthermore,
complex ceramic powders (for example used as cathode active materials in lithium ion batteries)
or oxide thin films (think about electron conducting layers in photovoltaics) are rarely considered
as ceramics. For all the above-mentioned reasons, ceramics are truly “hidden champions” in this
field.
Driven by the urgent need to limit the climate change induced by huge greenhouse gases
emissions, the shift from fossil-based energy supply to fluctuating renewables is progressing at a
global scale. Numerous studies, papers and books exist on this exciting and very complex topic of
the energy transitions [1,2]. They are indeed multiple scenarios depending on a large number of
factors including political decisions and incentives. Energy technologies are particular in the
sense that they are part of a crucial infrastructure. Important selection criteria are investment
and operation costs, efficiency, robustness towards dynamic operation and tolerance to
pollutants, as well as long-term reliability. This infrastructure should indeed be resilient and
operational for at least 20 years, and often much longer - just think about the general trend of
lifetime extension of many nuclear power plants. In a nutshell, nothing comparable with
consumer electronics and planned obsolescence.
Advanced ceramics for energy conversion and storage [3]
Advanced ceramics are to be found in numerous established and emerging energy technologies.
First, ceramic materials possess outstanding thermomechanical properties combined with a high
chemical stability which makes them irreplaceable for high-temperature applications. In gas
turbines, advanced ceramic matrix composites (CMCs) reinforced with fibers serve as
revolutionary, lightweight structural materials for static and even mobile parts. Ceramic layers
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such as environmental barrier coatings and thermal barrier coatings are essential for the
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protection of the underlying metallic or ceramic substrates from corrosion and extreme
temperatures, respectively. In nuclear power plants, ceramics are found as sintered nuclear
fuels, neutron control materials, moderators and barriers. Ceramics are also envisaged as host
materials to immobilize radioactive waste materials for extremely long times. Receivers for
concentrated solar power require materials which absorb sunlight, have a low emission and
withstand high temperatures. Ceramics - both as bulk parts and coatings - show again unique
performance for this technology. Ceramic fillers with high heat capacity are also used for thermal
energy storage.
Direct conversion of energy (energy harvesting) is also enabled by ceramic materials. For
example, waste heat associated with many human activities can be converted into electricity by
thermoelectric modules. Oxide ceramics are stable at high temperature and do not contain any
toxic or critical element. Piezoelectrics couple mechanical energy with electric energy, offering
the possibility to develop micro-power sources for sensors and electronic devices in hazardous
and harsh environments. Functional metal oxide ceramic layers act as essential electron
transport medium for both photovoltaics and photo-electrocatalytic water splitting.
Ceramic materials can possess high ionic and/or electronic conductivity too that makes them
attractive for electrochemical applications. This electric conductivity is achieved through the
design of defects by multiple substitution and doping strategies. High-temperature solid oxide
fuel and electrolysis cells (SOFC/SOEC), but also ceramic membranes for oxygen or hydrogen
separation from gas mixtures rely on such materials. Both oxygen and proton conductors are
interesting from this point of view. Finally, electrochemical storage in rechargeable batteries
heavily uses ceramics in the form of complex electrode active materials in state-of-the-art
lithium-ion cells and solid electrolytes and separators for emerging and future solid-state
batteries. Sodium chemistry offers an interesting alternative, complementary option to lithium
chemistry and is well represented by numerous ceramic compounds.
Opportunities for materials design
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Independently from the properties and applications targeted, there are common principles for
the design, synthesis, and further optimization of ceramic materials. These are the general
principles of solid-state chemistry for substitution by iso- or aliovalent ionic species, considering
tolerable atomic size ratio for structural stability and enabling the creation of point defects and
related changes in oxidation state for electrochemically active compounds. However, there is
often a trade-off between performance and stability. For example, the higher the flux through an
oxygen transport membrane material, the lower its thermochemical stability towards gases and
impurities present during operation [3]. Higher stability can be achieved in multicomponent
ceramics by increased configurational entropy, leading to complex compositions for temperature
resistant materials, cathode active materials for lithium ion batteries, catalysts etc. [4] And if one
phase cannot fulfill all requirements, the development of dual or triple phase composite
materials can be a paying strategy, as shown in Fig. 1.
Figure 1. Back Scattered Electron-SEM image of a composite oxygen transport membrane material
composed of Ce0.8Gd0.2O2 fluorite (white phase), FeCo2O4 spinel (black phase) and
(GdCe)(FeCo)O3 perovskite (grey phase) formed in-situ during sintering. Credits: L. Fischer, D. Sebold.
Due to the infinite number of compositional modifications, unchartered regions of complex
phase diagrams cannot be comprehensively investigated from an experimental point of view.
In addition, there is a difference between the expected properties of a single crystal or phase and
a real polycrystalline ceramic. The effect of pores, complex grain and phase boundaries and
related space charge layers, and eventually dislocations cannot be neglected and even dominates
very often the behavior of the ceramic materials. That’s why the use of modeling approaches
based on different theoretical frameworks and scales has been reinforced [5,6]. Ab-initio,
atomistic ansatz is used for the prediction of crystal properties, molecular dynamics for
simulations of charge transport, thermodynamics for phase stability, phase field or discrete
element modeling for the prediction of microstructure evolution, etc. As an example, prediction
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of charge transfer between ceramic electrolyte and cathode active material is shown in Figure 2.
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Complex interactions at the atomic level have to be considered [7]. These simulation tools can be
nowadays complemented by artificial intelligence and data informatics algorithms in order to
take advantage of the large amount of data already published, steadily collected, evaluated. This
approach offers new ways to guide the identification of novel materials that should then
synthesized and verified experimentally [8]. Nevertheless, serendipity will certainly further play a
role in the discovery of new ceramics and phenomena.
Figure 2. Atomic structure of a probable Li7La3Zr2O12LiCoO2 interface in an all-solid-state battery. (100)
and (10-14) are among the most favorable surfaces of Li7La3Zr2O12 and LiCoO2, respectively. Credits: L.Y.
Kuo, P. Kaghazchi.
On the importance of materials integration and processing
After the synthesis of ceramic powders (which is usually scalable, a clear advantage for oxide
solid electrolytes for solid-state batteries for instance), numerous processing routes have been
developed and are used in the industry for ceramic materials. We took recently the example of
yttria-stabilized zirconia (YSZ) to show how both layer thickness from a few atomic layers to thick
millimetric coatings and microstructure (from highly porous to fully dense) can be tailored by
appropriate processing routes [9]. However, a considerable amount of know-how, not
necessarily written in textbooks nor detailed in the scientific literature, is most of the time
required for accurate control and reproducibility of the processes and resulting materials
properties. A practice-oriented, digital handbook or wiki of ceramic processing, summarizing
decades of experience, would be very valuable to the scientific community and is to our
knowledge still missing.
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Integration of ceramic materials into devices is the key to successful transfer in the industry. A
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material with unprecedented properties is unfortunately useless if not compatible with others
when manufacturing a component. In some cases, an intermediate protective layer can offer
satisfying functionality, at the expense of simplicity and low total cost. Taking the example of
SOFCs, a gadolinium-doped ceria thin film needs to be added between lanthanum-strontium-
cobalt-iron-perovskite (LSCF) cathode and YSZ electrolyte to block the inter-diffusion and
formation of detrimental phases during sintering [10].
Huge amounts of energy are required for the consolidation and densification of ceramics at high
temperature. These lengthy steps do not vanish with the emergence of additive manufacturing,
as most of the time it actually means only shaping of a green ceramic part, likewise requiring an
appropriate high-temperature consolidation step [11]. Alternative sintering routes have been
therefore proposed in order to decrease time and temperature, assisted by electric fields and
currents, mechanical pressure, transient sintering aids, ultrafast heating [12-15]. As shown in Fig.
3 for lithium aluminum titanium phosphate (LATP) electrolyte, it is possible to densify ceramics at
much reduced temperatures compared to free sintering. They might for instance bring solutions
to the current challenge of co-sintering mixed cathode for solid-state batteries [16,17]. Still
stringent efforts are required to transfer the accumulated lab-scale experience to industrial mass
production, but I am confident that by choosing interesting business cases new sintering
technologies can make their way towards commercialization. Looking back at the development
of Field Assisted Sintering Technology / Spark Plasma Sintering over the last years, both
diversified product range and automatization have enabled to make use of such innovation.
Figure 3. Fracture surface of cold sintered LATP (Max. temperature: 500°C, Pressure: 300 MPa, 1
min dwell time, 1 M LiOH aqueous solution as sintering aid, FAST/SPS as heating unit). Credits: K.
Nur, D. Sebold
Alternatively, advanced coating techniques like plasma-spray physical vapor deposition (PS-PVD)
allow for unique microstructures and materials combination by evaporating ceramic particles in a
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hot plasma plume above 10,000 K. For instance, a dense hydrogen-transport ceramic membrane
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could be deposited on a porous metallic support with satisfying performance. [18]
On the importance of testing under realistic conditions
After having solved the challenge of materials integration, appropriate testing should be carried
out, mimicking possible real operation conditions, operando characterization and test of working
devices being of course the ultimate goal. Due to the long lifetime of energy infrastructure, this
demands long-term experiments in realistic environments (i.e. relevant temperature range and
mechanical loading, “dirty” atmospheres with the presence of water vapor, CO2, impurities etc.).
As first example, foreign particles like calcium-magnesium-aluminum-silicates (CMAS) are
particularly detrimental to high-temperature barriers as shown in Fig. 4, because they melt and
react with the ceramic coating [19]. Top layers are thus of limited applicability if they only offer
high resistance to water corrosion but poor stability in the presence of additional contaminants.
Figure 4. SEM cross-section of a porous plasma-sprayed YSZ Thermal Barrier Coating after
degradation in cyclic burner rig test with simultaneous CMAS deposition. Credits: R. Laufs, M.
Tandler, M. Kappertz, D. Sebold
Second, ceramic materials for batteries can be sensitive to air even at room temperature: some
cathode powders need to be handled in dry rooms with extremely reduced water vapor levels.
Lithium lanthanum zirconate garnet, a promising solid electrolyte, suffers from lithium-proton
exchange and formation of carbonates at its surface, leading to a rapid degradation of
properties. Fortunately, adequate thermal post-treatments can be carried out so that shaping
from water-based slurries can still be done in air, eliminating the large costs for a dry
environment as required for liquid organic electrolytes [20].
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Therefore, changes in mechanical, chemical, electrical, electrochemical properties should be
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thoroughly analyzed and related to the phenomena occurring at the microstructural level.
Diffusion, migration, depletion, formation of new phases, coarsening, etc. are common events
observed in ceramic based energy technologies after operation, cycling and/or exposure to
typical loadings. Owing to the targeted long lifetime and reliability, it is important to emphasize
that not only the first few cycles or the few hours are important: the performance should be
monitored over a larger number of cycles or longer period of time, with respect to the
requirements for operation [3].
As those tests are costly and mobilize infrastructure and man power, accelerated testing is
desirable. However, the difficulty lies in the fact that kinetics only should be modified, and not
the nature of the mechanisms involved. Modifying one or several of the testing parameters
(temperature, mechanical load, fuel concentration, current density, applied voltage, etc.) may
indeed trigger other phenomena which are inexistent under normal operation conditions! Early
detection, with more precise characterization tools coupled with simulations, could accelerate
the pace of research and development. But again, the whole technical system has to be
considered and not only one single material or layer. Exemplarily, steels used as interconnectors
and frames for the SOFC technology optimized for temperatures above 700°C failed when
employed at a lower temperature [21].
Conclusion
Due to their unique properties, ceramic materials are critical for many energy conversion and
storage technologies. In the high-temperature range typically above 1000°C (as found in gas
turbines and concentrated solar power), there is hardly any competition with other types of
materials. Under the harshest conditions, even new structural ceramic materials like CMCs [3]
and MAX phases [22] need protective layers, of course out of stable oxide ceramics. For other
applications, especially fuel cells and electrolysis, separation membranes and batteries, other
materials classes cannot be neglected. Some interesting options might rely on the combination
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of organic and inorganic materials, joining respective strengths and eliminating weaknesses in
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hybrid concepts. To rationally select analysis and a technology, the capital and operation costs as
well as Life Cycle Assessment of the whole technical system have to be considered. As mentioned
in the introduction, our future energy supply based on renewables will rely on numerous,
complementary technologies, where ceramics play for sure – either in mass or niche markets- an
important role. To conclude, new aspects related to concepts of circular economy should be
considered: repair of components, re-use and recycling of materials instead of throwing
everything away- this is also relevant for ceramic-based energy technologies!
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Figure captions
Figure 1. Back Scattered Electron-SEM image of a composite oxygen transport membrane material
composed of Ce0.8Gd0.2O2 fluorite (white phase), FeCo2O4 spinel (black phase) and
(GdCe)(FeCo)O3 perovskite (grey phase) formed in-situ during sintering. Credits: L. Fischer, D. Sebold.
Figure 2. Atomic structure of a probable Li7La3Zr2O12LiCoO2 interface in an all-solid-state battery. (100)
and (10-14) are among the most favorable surfaces of Li7La3Zr2O12 and LiCoO2, respectively. Credits: L.Y.
Kuo, P. Kaghazchi.
Figure 3. Fracture surface of cold sintered LATP (Max. temperature: 500°C, Pressure: 300 MPa, 1
min dwell time, 1 M LiOH aqueous solution as sintering aid, FAST/SPS as heating unit). Credits: K.
Nur, D. Sebold
Figure 4. SEM cross-section of a porous plasma-sprayed YSZ Thermal Barrier Coating after
degradation in cyclic burner rig test with simultaneous CMAS deposition. Credits: R. Laufs, M.
Tandler, M. Kappertz, D. Sebold
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