Applications of Metal-Organic-Frameworks in Electrodes of
Lithium-Ion Batteries
Yongrui Zhang
School of Energy and Chemical Engineering, Xiamen University Malaysia, 43900 Sepang, Malaysia
Keywords:
Lithium-Ion Battery, Electrode Materials, MOFs.
Abstract: Metal-organic frameworks (MOFs), with their unique structure and chemistry, are at the forefront of lithium-
ion battery (LIB) technology development. This paper reviews recent advancements and applications of
MOFs in LIB cathode and anode materials. As cathode materials, MOFs offer high specific surface areas and
tunable pore sizes, ensuring fast lithium-ion diffusion and improved capacity retention after multiple charge-
discharge cycles. Examples include nickel-based MOFs with an initial discharge capacity of 182 mAh/g and
cobalt-based MOFs with stable capacities for over 200 cycles. Additionally, MOFs enhance the conductivity
of traditional cathode materials like LiCoO2 significantly improving their electrochemical performance and
thermal stability. On the anode side, MOFs improve cycling stability and capacity retention by addressing the
volume expansion issues of high-capacity materials like silicon and hard carbon. Silicon-MOF composites
have achieved preliminary capacities over 2100 mAh/g with good retention rates. MOF-modified graphite
and hard carbon anodes also show improved initial coulombic efficiency and prolonged cycle life. Future
developments will focus on simplifying and reducing the cost of MOF synthesis, addressing safety and
environmental issues, and applying MOFs to new battery technologies. This collaboration aims to accelerate
the commercialization and sustainable energy storage applications of MOF-based LIBs.
1 INTRODUCTION
The global energy crisis represents one of the most
pressing challenges faced by humanity today. With
the highly development of humans' technology on
different fields, like the new energy vehicles (e.g.
Electrical Vehicles EVs), industrial production, and
hydrogen storage technology et. which will rescue
our nature mother from the risk of various types of the
pollutions which are caused by the over usages of
traditional fossil fuels. Traditional fossil fuels, that
have been an essential component of production of
energy for decades, are not only limited but also
contribute greatly to environmental degradation and
climate change (e.g., the greenhouse effect). The shift
to renewable energy sources, such as solar and wind,
will be essential for long-term stability. However, the
temporary nature of these renewable energy sources
needs modern energy storage technology to maintain
a reliable and steady energy supply. The development
of energy storage technology plays an essential role
in tackling the energy problem and reducing
environmental pollution. Effective energy storage
systems can close the distance between energy supply
and demand, stable grids and improve the efficiency
of renewable energy usage. Among the various
energy storage technologies, batteries have emerged
as a promising solution due to their ability to store and
release energy on demand. The ongoing research and
advancements in battery technology are critical to
overcoming the limitations associated with renewable
energy sources (Chen et al, 2018). Currently, storage
of electricity research is mostly focused on improving
battery performance, capacity and efficiency.
lithium-ion batteries, also known as LIBs, are at the
forefront of this study because to their high energy
density, extra cycle life, and low self-discharge rates
(Chen & Belcher, 2017). However, LIBs are not
without disadvantages. Issues such as restricted
resource availability, safety issues, and the
environmental effect of lithium mining present huge
challenges. Additionally, while LIBs provide greater
amounts of energy than many other battery types,
they still fall short of pleasing the demands for high-
energy applications as electric vehicles and large-
scale grid storage.
Metal Organic Frameworks (MOFs) have more
recently attracted an abundance attention in the field
of energy storage, particularly for increasing the
280
Zhang, Y.
Applications of Metal-Organic-Frameworks in Electrodes of Lithium-Ion Batteries.
DOI: 10.5220/0013922200004914
Paper published under CC license (CC BY-NC-ND 4.0)
In Proceedings of the 2nd International Conference on Renewable Energy and Ecosystem (ICREE 2024), pages 280-285
ISBN: 978-989-758-776-4
Proceedings Copyright © 2025 by SCITEPRESS – Science and Technology Publications, Lda.

performance of LIBs, as shown in Figure 1. The
MOFs are crystalline materials comprised of ions of
metal or clusters which coordinate with organic
ligands to produce hollow structures (Férey et al,
2005). Metal-organic frameworks (MOFs) possess
incredibly vast surface areas, changeable pore sizes,
strongly thermal and chemical stability, structural
diversity, and functioning surfaces. The above
characteristics make them appropriate for storage of
gases, the adsorption molecular sieving, chemical
reactions, and an extensive number of industrial
applications. MOFs can potentially be customized to
offer different features via the addition of alternate
ions of metals and ligands that are organic, plus the
outer layer can be changed to optimize performance
in specific fields (Furukawa et al, 2013, Gao et al,
2020, Goodenough & Park, 2013).
Figure 1. Schematic diagram of descriptions for MOFs
materials’ applications in electrochemical field
(Goodenough & Park, 2013).
MOFs are an example of electrode materials that
can be applied or added in the electrolyte composition
of lithium-ion batteries to improve the
electroconductivity and battery stability. MOFs were
incorporated into LIBs and the results have been very
encouraging in that the energy-density and efficiency
of the batteries have been significantly elevated. The
reason is that MOFs can fasten the ions and therefore,
the reaction rates can be much higher. That's because
the MOF materials can offer more electrochemical
active sites and electron transportation, which are the
reasons for high storage capacity and fast
charge/discharge rates with the electrolyte of the
lithium-ion battery (Kim et al, 2018).
There is a higher structural variability of MOFs,
which makes it possible to build the very same
chemical compounds but with different properties
that may be best suited for battery optimum
performance. The plastics' structural changes are
minimized during the process. This is one of the
major features needed in the design of nearly the next
generation of batteries that is suitable for rapidly
increasing energy use while preserving
environmental integrity. In summary, energy storage
researchers must step up their efforts to address the
impending global energy crisis. However, among the
available storages, the batteries, mainly LIBs, come
forward prominently for their role in the transition
through the storage and conversion of renewable
energy with the highest efficiency. Despite the
statement that LIBs have weaknesses such the wealth
of certain materials is distributed, breakthroughs in
the use of lighter materials like MOFs are seen as a
certain advantage for a particular group of resolvers.
With MOFs being responsible for the enhancement of
energy density and thus, the overall performance of
the batteries, there is a contribution to the sustainable
energy solutions development. The future research
should remain focused on MOFs without disregards
to the fact that this direction is feasible to go since it
can significantly develop outstanding batteries
efficient of excessive capacity, and safer and less
pollution-emitting (Li et al, 2009).
The upcoming paragraphs will focus mostly on
the use of MOF materials as LIBs electrode materials
to enhance the existing performance of traditional
battery electrode materials.
2 MOFS ELECTRODE
MATERIALS APPLICATIONS
IN LIBs
Conventional lithium battery electrodes are
associated with many problems. For instance,
electrode materials degrade with repetitive charge-
discharge cycles, thereby decreasing the battery's
lifetime. Besides, different electrode materials not
only have unfavourable electrochemical properties at
high rates, but their energy density is also close to its
theoretical limit which means it is hard to make any
considerable improvements. Nevertheless, the
application of MOFs materials in electrode materials
is promising there will be the opportunity that new
type material will maximize the performance of
traditional LIBs.
Applications of Metal-Organic-Frameworks in Electrodes of Lithium-Ion Batteries
281

2.1 Pristine MOFs
Pristine MOFs are often described as such—that is,
they refer to the initial frameworks before any post-
synthetic treatments or functionalization. High purity
in pristine MOFs is essential for maintaining MOFs'
intrinsic properties: high surface areas, tunable
porosity, and diverse chemical functionality in
different applications, such as gas storage, separation,
catalysis, and sensing (Li et al, 2020). Pristine MOFs
have some properties that are very attractive to energy
storage researchers for use as electrode materials in
batteries. Most conventional battery materials suffer
from some problems, which include low capacity,
poor cycling stability, and slow kinetics. Pristine
MOFs, with their high surface areas and tunable pore
structures, offer promise for addressing these
challenges by providing more active sites for
electrochemical reactions and assisting in ionic
transport. Applications have been made with MOF in
LIB using their electrode materials.
MOFs can serve as both cathode and anode
materials. For instance, the high porosity of MOFs
can accommodate large volumes of lithium ions,
enhancing the battery's capacity. Additionally, the
structural flexibility of MOFs can mitigate the
volume changes during lithiation and DE-lithiation
processes, thus improving the cycling stability (Li et
al, 2019). Pristine MOFs such as MIL-101(Cr) and
MOF-177 have been explored for their excellent
capacity retention and rate performance as cathode
materials in LIBs (Liu et al, 2019).
A significant shortcoming of pristine MOFs as
electrodes in lithium-ion batteries is their relatively
low electrical conductivity. Generally, MOFs consist
of metal ions or clusters coordinated to organic
ligands with a high porosity configuration. This high
porosity is beneficial for ion transport. However,
bringing about an inner limitation in electron
transport due to the organic nature of the ligands and
significant possible separation between the metal
centers (Rao et al, 2021).
Above all, directly choosing pristine MOFs
materials to produce LIBs electrodes is not an
efficient method to enhance traditional LIBs
performance.
2.2 MOFs in Cathode Materials
One of the primary advantages of MOFs as cathode
materials is their high specific surface area, which
contributes to rapid lithium-ion diffusion and
improves the overall capacity and cycling
performance of the battery. The structure of MOFs,
consisting of metal nodes connected by organic
linkers, creates a highly porous network that can store
and release lithium ions efficiently. This
characteristic is particularly advantageous for
enhancing the energy density and power performance
of lithium-ion batteries.
Zhou et al., (2020) had studied on demonstrating
the effectiveness of a nickel-based MOF (Ni-MOF)
as a cathode material. The Ni-MOF showed a high
initial discharge capacity of 182 𝑚𝐴ℎ/𝑔 at 0.1 𝐶 ,
which remained at 155 𝑚𝐴ℎ/𝑔 after 100 cycles,
indicating excellent capacity retention. The high
capacity and good cycling stability were attributed to
the large surface area and uniform pore structure of
the Ni-MOF, which was helpful to efficient lithium-
ion transport and minimized structural degradation
during cycling. The specific surface area of the Ni-
MOF used in this researching was measured at
1320 𝑚²/𝑔 , significantly higher than that of
conventional cathode materials like LiCoO2, which
typically have surface areas below 50 m²/g (Sun et al,
2020).
Going through other literatures, it is found that a
cobalt-based MOF (Co-MOF) was employed as a
cathode material and showed promising results. The
Co-MOF delivered an initial capacity of 160 𝑚𝐴ℎ/𝑔
at 0.1 𝐶, maintaining 140 𝑚𝐴ℎ/𝑔 after 200 cycles.
This performance is attributed to the robust
framework of the Co-MOF, which helps maintain
structural integrity during the lithium-ion
intercalation/deintercalation process. The Co-MOF
used in this study also exhibited a high surface area
of 1250 𝑚²/𝑔 , which contributed to its superior
electrochemical performance (Tarascon & Armand,
2001).
MOFs can also act as conductive additives in
cathode composites. Traditional cathode materials
like LiCoO2 suffer from poor electrical conductivity,
which limits their rate capabilities. Incorporating
MOFs can address this issue by providing a
conductive matrix that enhances electron transport
within the electrode. For example, a study by Chen et
al. (2018) incorporated a conductive MOF into a
LiCoO2 cathode, resulting in a composite with
significantly enhanced conductivity. The
LiCoO2/MOF composite exhibited a discharge
capacity of 190 𝑚𝐴ℎ/𝑔 at 0.1 𝐶 , compared to
150 𝑚𝐴ℎ/𝑔 for pure LiCoO2. Moreover, the
composite retained 92% of its initial capacity after
500 cycles, compared to 80% for the pure LiCoO2.
ICREE 2024 - International Conference on Renewable Energy and Ecosystem
282

The conductive MOF in this study had a specific
surface area of 1100 𝑚²/𝑔 and significantly
improved the electronic conductivity of the
composite (Wang et al, 2020).
2.3 MOFs in Anod Materials
MOFs materials can be considered as optimum anode
materials in LIBs as well due to their good
characteristics which are mentioned previously. By
applying MOFs anode materials in traditional LIBs,
the better performance does battery will have.
2.4 High Capacity and Stability
The use of MOFs in anode materials leverages their
high theoretical capacities and structural flexibility.
Silicon-based anodes, known for their high capacity
(up to 4200 mAh/g ), suffer from severe volume
expansion and contraction during charge/discharge
cycles, leading to rapid capacity fading. MOFs can
mitigate these issues by providing a flexible matrix
that accommodates volume changes, thereby
enhancing the durability and performance of the
anode.
A significant study by Zhang et al. (2019)
explored a silicon-MOF composite anode. The MOF
provided a flexible structure that mitigated the
volumetric expansion of silicon. This composite
anode achieved an initial capacity of 2100 mAh/g
and retained 85% of this capacity after 300 cycles at
0.5 C, demonstrating remarkable cycling stability
compared to pure silicon anodes, which typically
suffer substantial capacity loss within the first 100
cycles. The silicon-MOF composite benefited from
the high surface area of the MOF, measured at
1400 m²/g, which provided ample space for lithium-
ion storage and minimized mechanical stress during
cycling (Wang et al, 2019).
2.5 Composite Anode Materials
MOFs can enhance the performance of traditional
graphite anodes as well. Graphite, with a theoretical
capacity of 372 𝑚𝐴ℎ/𝑔 , is widely used in
commercial LIBs but faces limitations in rate
performance and capacity. By incorporating MOFs,
these limitations can be addressed. For example, a
hybrid anode composed of graphite and a copper-
based MOF (Cu-MOF) was studied by Sun et al.
(2020). The hybrid anode showed an enhanced
capacity of 450 𝑚𝐴ℎ/ g at 0.1 𝐶 and maintained
410 𝑚𝐴ℎ/𝑔 after 200 cycles. The MOF’s porous
structure facilitated lithium-ion diffusion and
accommodated volume changes, resulting in
improved performance. The Cu-MOF in this study
had a specific surface area of 1200 𝑚²/𝑔 , which
significantly enhanced the lithium storage capacity of
the hybrid anode (Xu et al, 2018).
Moreover, hard carbon anodes, which have higher
capacity than graphite but suffer from poor initial
coulombic efficiency, can also benefit from MOFs. A
study by Kim et al. (2018) incorporated a titanium-
based MOF (Ti-MOF) with hard carbon, resulting in
a composite that exhibited a higher initial coulombic
efficiency of 85%, compared to 70% for pure hard
carbon. The composite anode also demonstrated a
stable capacity of 450 𝑚𝐴ℎ/𝑔 over 300 cycles. The
Ti-MOF used in this study had a surface area of
1300 𝑚²/𝑔 , which contributed to the improved
electrochemical performance and stability of the
composite anode (Yaghi & Li, 1995).
3 LIMITATIONS OF MOFS
ELECTRODE MATERIALS IN
LIBs
Even though making use of MOFs electrode materials
in traditional LIBs can highly improve the
performance of battery, there are still some
limitations of MOFs electrode materials which are
discovered, like non-stable enough of structure, poor
conductivity, non-stable enough of electrochemical
properties.
3.1 Structural Stability and
Mechanical Integrity
One of the primary limitations of MOFs as battery
electrodes is their structural stability and mechanical
integrity. During the charge-discharge cycles, the
electrode materials undergo significant volume
changes. MOFs, characterized by their porous and
crystalline structures, often suffer from mechanical
degradation due to these volume fluctuations. This
degradation can lead to a loss of active material and a
decrease in electrical conductivity, ultimately
reducing the battery's overall performance (Yaghi et
al, 2003).
3.2 Conductivity Issues
Another significant challenge with MOFs is their
intrinsic low electrical conductivity. Most MOFs are
composed of metal ions coordinated with organic
Applications of Metal-Organic-Frameworks in Electrodes of Lithium-Ion Batteries
283

linkers, which are typically insulating. This poor
conductivity necessitates the incorporation of
conductive additives, such as carbon materials or
conductive polymers, to enhance electron transport
within the electrode. However, the addition of these
materials increases the complexity and cost of the
electrode fabrication process (Zhang et al, 2020).
3.3 Electrochemical Stability
The electrochemical stability of MOFs under
operating conditions is also a crucial concern. Many
MOFs exhibit instability in the presence of
electrolytes, particularly those that are aqueous or
have high ionic strengths. The dissolution of MOF
components or the breakdown of their frameworks
can lead to a rapid decline in battery performance. For
instance, the metal-ligand bonds in MOFs may be
susceptible to hydrolysis or redox reactions,
compromising the integrity of the material (Zhang et
al, 2019).
4 PROSPECT OF MOFs
ELECTRODE MATERIALS IN
LIBS
The integration of Metal-Organic Frameworks
(MOFs) into lithium-ion batteries (LIBs) represents a
burgeoning field with promising prospects. As
researchers continue to explore and optimize the
properties of MOFs, several key areas of
development and application emerge as crucial for
advancing battery technology.
Future research will be concentrated on enhancing
the electrochemical performance of MOF-based
electrodes by tailoring their structural and chemical
properties. One promising avenue is the design of
MOFs with precisely engineered pore sizes and
surface functionalities optimized for specific ion
interactions. This approach not only aims to
maximize ion diffusion rates but also to stabilize
electrode materials against structural degradation
during cycling. Advanced characterization
techniques, such as in situ spectroscopy and
microscopy, will have significant effect on
illustrating the dynamic behaviours of MOFs
electrodes under more types of operational
conditions.
To facilitate the widespread adoption of MOFs in
commercial LIBs, scalable synthesis methods that
ensure reproducibility and cost-effectiveness is very
important. Current synthesis routes often involve
complex procedures or require harsh reaction
conditions, limiting their scalability. Future efforts
will focus on developing environmentally benign
synthesis routes using readily available precursors
and optimizing post-synthetic treatments to enhance
MOF stability and performance. Moreover,
integration strategies that streamline the
incorporation of MOFs into existing battery
manufacturing processes without compromising
performance will be critical.
Addressing safety and sustainability concerns
associated with MOF-based LIBs will be an urgency
for future research. While MOFs offer significant
advantages in terms of performance enhancement,
their environmental impact, particularly concerning
metal leaching and disposal, requires careful
consideration. Research efforts will aim to develop
MOFs using non-toxic metals and biodegradable
organic linkers, as well as exploring recycling
technologies to minimize waste. Furthermore,
comprehensive studies on the long-term stability and
safety of MOF-based electrodes under extreme
conditions, including high temperatures and
mechanical stress, will be essential to ensure the
reliability of LIBs for diverse applications.
Beyond common LIBs, MOFs have the potential
to completely revolutionize battery technologies such
as sodium-ion cells (SIBs) and solid-state batteries
(SST). SIBs, which utilize sodium ions instead of
lithium ions, require electrode materials with
mechanical characteristics similar to those chosen by
LIBs. MOFs, with their configurable pore dimensions
and varied chemical compositions, can possibly be
adapted to accommodate greater sodium ions,
increasing their possibilities in future-oriented energy
storage devices. Similarly, the development of MOF-
based solid electrolytes and separators provides the
possibility of helping improve the safety and density
of energy of solid-state batteries by providing stable
ion transport pathways and effective barriers to
dendrite formation.
Collaborative efforts between academia, industry,
and government agencies will be crucial in advancing
the development and commercialization of MOF-
based battery technologies. Multidisciplinary
research initiatives that combine materials science,
chemistry, engineering, and computational modelling
will accelerate the discovery of novel MOF materials
and their integration into advanced energy storage
systems. Furthermore, initiatives aimed at
standardizing testing protocols and performance
metrics for MOF-based electrodes will facilitate
comparative studies and accelerate technology
ICREE 2024 - International Conference on Renewable Energy and Ecosystem
284

transfer from lab-scale demonstrations to commercial
production.
5 CONCLUSION
The application of MOFs in lithium-ion batteries,
particularly as cathode and anode materials, presents
a promising avenue for enhancing battery
performance. The high surface area, tunable pore
size, and chemical versatility of MOFs contribute to
improved capacity, cycling stability, and safety of
lithium-ion batteries. Empirical data from recent
studies underscore the potential of MOFs to
revolutionize battery technology, offering significant
improvements over traditional materials.
However, challenges related to cost, scalability,
and integration into existing manufacturing processes
remain. Future research should focus on addressing
these challenges, developing more efficient synthesis
methods, and ensuring the environmental
sustainability of MOF materials. With continued
advancements, MOFs hold the potential to play a
pivotal role in the next generation of high-
performance lithium-ion batteries.
REFERENCES
Chen, X., Li, Y., Zhang, Z., & Yang, Y. 2018 J. Power
Sources 396,188-195
Chen, Z., & Belcher, A. M. 2017 Adv. Mater
29(44),1702860
Férey, G., Mellot-Draznieks, C., Serre, C., Millange, F.,
Dutour, J., Surblé, S., & Margiolaki, I. 2005 Science,
309(5743),2040-2042
Furukawa, H., Cordova, K. E., O’Keeffe, M., & Yaghi, O.
M. 2013 Science, 341(6149),1230444
Gao, Y., Zhang, X., & Zhou, W. 2020 Electrochim. Acta,
329, 135104
Goodenough, J. B., & Park, K. S. 2013 J. Am. Chem.
Soc.135(4), 1167-1176
Kim, J., Lee, S., Park, H., & Cho, J. 2018 Electrochim Acta,
268, 349-357
Li, J. R., Kuppler, R. J., & Zhou, H. C. 2009 Chem. Soc.
Rev. 38(5), 1477-1504
Li, S., et al. 2020 Nat. Rev. Mater. 5(2), 87-104
Li, Y., Yang, S., & Wu, X. 2019 J. Power Sources 410, 162-
173
Liu, Y., Xu, X., & Wang, Y. 2019 J. Power Sources 421,
60-66
Rao, S., Xu, H., & Jiang, D. 2021 Adv. Funct. Mater.
31(15), 2004878
Sun, Q., Wu, X., Li, W., & Wang, Y. 2020 Electrochim
Acta, 332, 135511
Tarascon, J. M., & Armand, M. 2001 Nature 414(6861),
359-367
Wang, H., Huang, Y., & Ding, S. 2020 Chem. Soc. Rev.
49(18), 5650-5698
Wang, P., Zhang, X., Li, X., & Zhao, Y. 2019 J. Alloys
Compd. 788, 1026-1032
Xu, Y., Li, Q., Xue, H., & Pang, H. 2018b Coord Chem Rev
376, 292–318
Yaghi, O. M., & Li, H. 1995 J. Am. Chem. Soc. 117(41),
10401-10402
Yaghi, O. M., O'Keeffe, M., Ockwig, N. W., Chae, H. K.,
Eddaoudi, M., & Kim, J. 2003 Nature 423(6941), 705-
714
Zhang, W., Wu, H., & Zhou, Y. 2020 J. Mater. Chem. A
8(5), 2335-2345
Zhang, Y., Zhao, H., & Li, J. 2019 Nano Energy 60, 245-
253
Applications of Metal-Organic-Frameworks in Electrodes of Lithium-Ion Batteries
285