Electrochemistry Communications 122 (2021) 106881

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Recent advances in lithium-based batteries using metal organic frameworks

as electrode materials
Yongchao Jiang a, b, 1, Haitao Zhao a, 1, Luchao Yue a, Jie Liang a, Tingshuai Li a, Qian Liu a,
Yonglan Luo a, Xiangzhe Kong b, Siyu Lu c, Xifeng Shi d, Kun Zhou b, *, Xuping Sun a, *
a
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China
b
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, Sichuan, China
c
Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou 450001, Henan, China
d
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, Shandong, China

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

Keywords: Metal organic frameworks (MOFs) show excellent electrochemical performances due to their ultrahigh porosity,
MOFs large specific surface area, and easy functionalization. These characteristics make it fascinating electrode ma­
MOF composites terials with excellent electrochemical performance for the currently dominated lithium-based batteries (e.g., Li-
MOF-derived materials
ion batteries, Li-S batteries, Li-O2 batteries). Hence, this review summarizes the recent advances of MOFs-based
Li-ion batteries
Li-S batteries
materials as an electrode for high-performance lithium-ion storage. Firstly, we briefly describe the development
Li-O2 batteries history, principle, and mechanism of the lithium-based batteries. Then, the recent advances of MOFs/MOFs
composite and MOF-derived materials employed as electrode materials for Lithium-ion batteries, Li-S batteries,
and Li-O2 batteries are reviewed with their electrochemical performances. Finally, we conclude and point out the
future direction of MOFs-related materials for lithium-based batteries.

1. Introduction electrochemical (redox and catalytic activities) performance.

The electrochemical energy storage (EES) technique is the most
promising solution to alleviate the depletion of fossil fuel and maximize
the utilization of renewable energy [1]. The rapid advances of EES
technology stem from the contradiction between the fluctuation of
sustainable energy supply and the growth of mobile power demand [2].
The rapid development of portable EES devices stimulates the demand
for high energy density systems, such as secondary batteries (e.g., Li-ion
batteries (LIBs) [3–7], Li-S batteries [8–11], Li-O2 batteries [12–15], etc.
[16–19]). LIBs are receiving increased attention due to their excellent
energy density, long usage time, and low weight. Similarly, Li-S and Li-
O2 batteries with high theoretical energy density (approximate 5 to 10
times higher than the LIBs) also show the potentials as promising energy
storage devices [20]. However, massive research efforts demonstrated
that the electrochemical performance of lithium-based batteries mainly
depended on the electrode materials; therefore, the main challenges for
excellent lithium storage devices lies in finding adequate electrode
materials with highly electronic, ionic conductivity as well as superior
Currently, various materials have been investigated as the electrode
for lithium-based batteries, such as carbon materials, alloying materials,
and metal compounds [21–24]. Owing to high pore volume and excel­
lent electronic conductivity, carbon materials such as carbon nanotubes
(CNTs) and graphene are considered attractive electrode or supporter
materials for lithium-based batteries [25,26]. In terms of alloying ma­
terials and metal compounds, the high specific capacitance could be
achieved, but their cycling life and rate capacity are relatively poor.
Unlike the above-mentioned materials, metal–organic frameworks
(MOFs) have flourished as promising platforms for designing advanced
electrode materials of lithium-based batteries due to their diversity and
controllable structures of MOFs/MOF composites and MOF-derived
materials [27–32]. Detailedly, MOFs and MOF-related materials
exhibited several superiorities when used as the electrode for lithium-
based batteries: (i) the intrinsically porous structure of MOFs is benefi­
cial to the penetration of electrolyte and efficiently tolerate the volume
expansion during storage lithium ions [33]; (ii) their designable com­
ponents promise the incorporation of electroactive sites, enabling

* Corresponding authors.
E-mail addresses: kunzhou925@163.com (K. Zhou), xpsun@uestc.edu.cn (X. Sun).
1
Both authors contributed equally to this work.

https://doi.org/10.1016/j.elecom.2020.106881
Received 9 October 2020; Received in revised form 18 November 2020; Accepted 22 November 2020
Available online 26 November 2020
1388-2481/© 2020 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
Y. Jiang et al.
infinite possibilities for the search of candidate electrode materials for
different battery systems [2,34]; Nevertheless, just like a double-edged
sword, the inferior electronic conductive and low tap density MOFs
limit their practical application for different battery system. What’s
more, MOFs also suffer from seriously irreversible structural collapse
during the lithium ion storage process. on another hand, MOF-derived
materials obtained by using MOFs as self-sacrificial templates inherit
the porous structures of MOF precursors and display excellent electronic
conductivity offered by the carbon component, exhibiting more promise
as electrode materials [20,35–37]. Overall, MOFs are considered to be a
most prospective candidate for lithium ion storage [38].
At present, some high-quality reviews on MOFs for electrochemical
application are mainly focused on electrochemistry [39], energy storage
[40], direct electrochemical applications [41], and LIBs [42]. However,
MOFs used as promising electrode materials for the lithium-based bat­
teries are rarely comprehensively reported. Moreover, with the devel­
opment of MOFs with various structure and coordination metal center,
enormous progress of lithium-based batteries has been made in recent
decade. Consequently, we review the recent research development of
MOFs and MOF composites in lithium-based batteries by focusing on the
electrodes.
In this review, we first discussed the principle and history of lithium-
based batteries briefly. Subsequently, we emphasized the applications of
MOF materials as promising materials for LIBs and Li-S batteries as well
as Li-O2 batteries. Even, we also reported MOF materials as solid-state
electrolytes and separators for lithium-based batteries. At the end, we
also point out the research prospects and challenges in this field.
2. Fundamentals of lithium-based batteries
2.1. The development of lithium-based batteries
Lithium-based batteries are mainly divided into three categories:
LIBs, Li-S batteries, Li-O2 batteries. Moreover, in a large number of en­
ergy storage technologies[43–45], LIBs can become a research focus in
energy storage systems due to their outstanding specific energy and
Fig. 1. (a) Brief summary of the development history of LIBs; Schematic representations of (b) LIBs, Reproduced ref. [1]. (c) Li-S batteries. Reproduced ref. [11]. (d)
Li-O2 batteries. Reproduced ref. [15].
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energy density [46,47]. Historically, Lewis and Keyes reported a battery
similar to lithium metal battery (LMB) firstly in 1913 [48]. Until 1965,
Selim and his colleagues tried to use the more common lithium metal
anode in propylene carbonate-based electrolytes [49]. Vissers’ group
[50] and Gay’s group [51] searched Li and Li-Al alloy or FeS2 systems at
high temperature (450 ◦ C) in the mid-1970 s. In 1980, Goodenough and
his colleagues discovered a layered oxide compound, namely lithium
cobalt oxide (LiCoO2). It can double the potential of LIBs. Even,
compared with TiS2, it also showed superb electrochemical reversibility
[52]. In the next 30 years, the LiCoO2 has become an almost unmatched
commercial cathode material. In 1991, Sony has commercialized a new
generation of lithium-ion batteries with carbon as the anode and LiCoO2
as the cathode. This is the world’s first commercial LIBs. In 1996, Padhi
and Goodenough discovered a phosphate with olivine structure
(LiFePO4) [53]. The high temperature resistance and overcharge resis­
tance of the phosphate are far superior to the traditional lithium ion
battery materials, so it has been used in automobile power battery,
medical equipment power supply, mobile power supply, and other small
electrical equipment suitable for large current discharge. With the
continuous breakthrough in the research and development of LIBs, the
LIBs industry as a high and new technology in the 21st century, will
continue to flourish for a long time in the future. At the time, the LIBs
had a good volumetric energy density (200 Wh L− 1) and an excellent
gravimetric energy density (80 Wh kg− 1). And these are better than
other rechargeable batteries of that era [54]. The revolutionary changes
in LIBs in the field of portable electronic devices have led to an explosive
growing interest in research (Fig. 1a) [2].
2.2. The principle of lithium-based batteries
Over the past three decades, lithium-based batteries technologies
have made remarkable progress in industry and academia [55–57].
Firstly, LIBs have been commercialized owing to their great advantage
in electric vehicles, electronics, energy storage, and renewable energy
storage. The schematic representations of LIBs are shown in Fig. 1b.
When LIBs are charged, Li+ is deintercalated from the cathode, then the
Y. Jiang et al.
deintercalated Li+ removes through the electrolyte into the anode; LIBs
will gain and store energy. When LIBs are discharged, the Li+ removes
back to the cathode; LIBs will release stored energy. In the field of
batteries, Li-S batteries can be a hope energy-storage solution, which can
use sulfur as the active cathode material to reversibly react with lithium
[58,59]. The schematic representation of Li-S batteries is shown in
Fig. 1c. When it discharges, various polysulfides are formed by reducing
S at the cathode, and these polysulfides combine with lithium to form
Li2S. However, the shuttle effect of the dissolved polysulfides in the
electrolyte solvents has influenced the electrochemical properties of Li-S
batteries. The shuttle mechanism: the soluble polysulphides are first
brought from the cathode to the anode where they will be reduced;
subsequently, these reduced products are removed to the cathode where
these reduced products will be reoxidized; and these oxidation products
are moved back to the anode to form different types of polysulphides,
then these polysulphides will be combined with lithium to form Li2S
[60]. Finally, Li-O2 battery has two types: Li-O2 battery based on non-
aqueous and aqueous electrolytes. The schematic diagram of Li-O2
batteries is shown in Fig. 1d. During discharging, at the cathode, the
lithium metal will be oxidized, releasing lithium ions into the electro­
lytes, and the charging process is the opposite. At the cathode, oxygen
first enters the porous cathode from outside world, then O2 will be
dissolved in the electrolytes, and finally it is reduced on the electrode
surface [60].
LIBs are composed of three basic components: an anode electrode, a
cathode electrode, and an electrolyte. The cathode electrode is usually
made of lithium transition metal oxides, while the anode electrode is
made of carbonaceous materials such as activated carbon [61,62].
Generally, Li-metal has high reactivity in water, so LIBs will be assem­
bled with electrode materials separated by non-aqueous electrolytes
(mainly composed of organic carbonate). However, the ionic conduc­
tivity of these electrolytes is usually very low, resulting in a small
spacing between the electrodes. During the first charge, the battery will
consume about 5–20% of lithium [63]. The reason for lithium con­
sumption is the production of a solid electrolyte interface (SEI).
Although the SEI may cause the loss of lithium, this is only a small part of
the consumption in the previous cycle. In addition, the presence of SEI in
LIBs is crucial, because the SEI layer can protect the battery during
overpotential and prevent material decomposition [64]. Compared with
LIBs, Li-S batteries also have a number of significant advantages, such as
the large amount of sulfur resources and excellent theoretical energy
density [65]. But, Li-S batteries still have some problems, especially the
‘‘shuttle phenomenon” of polysulfides. This shuttle mechanism can be
solved by using outstanding electrochemical material. Therefore, re­
searchers need to start from this aspect to enhance their electrochemical
performance. Furthermore, compared with LIBs and Li-S batteries, Li-O2
batteries have ultra-high theoretical energy density. Li-O2 batteries are
the main development direction of secondary batteries in the future.
And Li-O2 batteries will bring a huge promotion to the field of energy
storage. However, Li-O2 batteries still have some problems. For example,
if the cathode is covered by environmental air, it will be influenced by
H2O and CO2 to form LiOH and Li2CO3. Finally, it can not form Li2O2.
This will cause the cathode to be damaged to varying degrees. Thus, it is
necessary to take some protective measures (e.g., a special membrane,
special catalyst materials) which can prevent CO2 and H2O from
entering the cathode. Therefore, the superb electrochemical material
not only improves the electrochemical performance of lithium-based
batteries, but also makes lithium-based batteries better commercial­
ized. Hence, because of their Excellent property (e.g., adjustability,
porosity, and large specific surface area), MOF materials can become a
potential candidate as electrode materials in lithium-based batteries.
2.3. The mechanism related to MOFs and their composites for lithium-
based batteries
Up to now, MOFs as electrode materials for LIBs have been widely
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reported [66,67]. And they also exhibit excellent electrochemical per­
formance. However, their lithium ion storage performance can be
largely influenced by the energy storage mechanism of MOFs. Therefore,
it is very significant to exploit the high-performance MOFs by studying
the MOFs energy storage mechanism in deep. Energy storage mechanism
has been reported so far, include: (1) conversion mechanism, (2) inter­
calation mechanism, (3) absorption and desorption mechanism.
The conversion mechanism is based on the valence rise and fall of the
metal center in the MOFs structure for effective ion storage. It can be
divided into reversible conversion mechanism and irreversible conver­
sion mechanism according to whether there is metal element produc­
tion. During the irreversible conversion reaction, the formation of
elemental metal causes irreversible damage to the structure of MOFs.
Even, after the first charge and discharge, the pulverization of the
structure occurs, which limits the capacity of MOFs to a certain extent.
This will cause their first week of coulombic efficiency to become poor.
For example, Li et al. [68] researched MOF-177 [Zn4O(1, 3, 5-benze­
netribenzoate)2] as electrode material for LIBs. The reaction mechanism
is as formula (1) - formula (3):
Zn4 O(BTB)2 ⋅(DEF)m (H2 O)n + e + Li+ →Zn + Li2 O (1)
DEF + H2 O + e + Li+ →Li2 (DEF) + LiOH (2)
Zn + Li+ + e ↔ LiZn (3)
Obviously, formula (1) is an irreversible reaction that produces
elemental Zn; formula (2) only contributes to the capacity of the first
week; formula (3) is reversible and can provide a reversible capacity
source for the electrode. For the reversible conversion mechanism, when
the metal center undergoes a conversion reaction, only the valence rises
and falls without the formation of metal element, and its reversible
performance is also greatly improved. For example, Jin et al. [69] syn­
thesized Fe-based MOFs (MIL-88B), and found that its reversible lithium
storage mechanism is the reversible electrochemical conversion reaction
of Fe3+/Fe4+.
About the intercalation mechanism: the reversible energy can be
stored by opening and re-bonding the unsaturated bonds in the elec­
trochemical reaction process, since the organic ligand in the structure
contains unsaturated bonds. Moreover, the electrode materials of MOFs
with higher capacity can be obtained by selecting different types of
unsaturated bonds and increasing the number of active sites. For ab­
sorption and desorption mechanism, it usually does not form chemical
bonds on the electrode surface through electrostatic action. However, its
capacity usually is low.
MOF is a promising material as host material for Li-S batteries. When
MOF is used as host material, the mechanism of Li-S batteries does not
change much. Yet, MOFs can play some important roles, such as pre­
venting the shuttle of polysulfides and fixing sulfur [70,71]. MOFs are
also mainly used as catalysts for Li-O2 batteries, due to their pore
structure and a large number of accessible active sites. Because MOFs
can achieve high catalytic activity of ORR and OER, and their porous
structure diffuses active substances such as Li+ and O2 [72,73].
3. Application of MOF materials in LIBs
In recent years, LIBs became the representative of new energy stor­
age technology due to their superb storage energy density and good
electrochemical performance [74,75]. MOFs have been used as elec­
trode materials in LIBs because of their ultrahigh porosity, adjustable
pore structure, and high surface area [76]. Their ultrahigh porosity and
adjustable pore structure are advantageous to interface charge trans­
port. Furthermore, compared with pure organic materials, MOFs have
better thermal stability. Hence, more and more researchers have studied
MOFs as electrode materials for LIBs (Table 4).
Y. Jiang et al. Electrochemistry Communications 122 (2021) 106881

3.1. MOFs and their composites as electrode materials
Over the last several years, MOFs with abundant micro/nano-sized
pores or mesopores can make store ions by reversibly inserting/de-
inserting into the pores of aqueous solutions or organic electrolytes.
Even, the redox of metal ion clusters in them can also construct a path
for electron mobility. Thus, MOFs have been extensively studied as
promising candidates for electrode materials. However, MOF electrode
is impeded by many challenging issues, including the low conductivity
and poor electrochemical performance of different kinds of MOFs.
Therefore, MOFs can combine with other materials with remarkable
property, such as carbon-based materials[77–79], semiconductor silicon
[80], phosphorus[81]. Mainly because the carbon-based materials
possess high electrical conductivity and layered structure. The semi­
conductor silicon and phosphorus have very high theoretical capacity.
Even, phosphorus similarly obtains the unique layered structure.
Furthermore, when it be used as carrier, the unique layered structure of
material can avoid reunion and provides volume space for expansion
Thus, the conductivity and the electrochemical stability of MOF com­
posites can be enhanced.
3.1.1. Fe-MOFs and their composites as electrode materials
At first, researchers focused on Fe-based MOFs as electrode materials
for LIBs.[82–85] MOF can improve Li+ ions storage by adapting to better
lithium insertion/extraction. MOFs can tolerate the lithium insertion/
extraction strain. Furthermore, MOFs as electrodes can increase the
performance of LIBs. Their composites also retain excellent electro­
chemical properties as electrode for LIBs.
Fe-based MOFs have been studied as electrode material by re­
searchers because of their remarkable electrochemical properties [52].

Fig. 2. (a) Recapturing the temperature-driven structural evolution of the MIL-53(Fe)_quinone1 phase as a function of the heating conditions. Reproduced ref. [82].
(b) Crystal structure of the MIL53(Fe)-F0 described in the C2/c and P-1 unit cells with hydroxyl bridging ligands (OH) along the inorganic. Reproduced ref. [83]. (c, d)
SEM and TEM images of the as-synthesized coordination polymers. Reproduced ref. [86]. (e) Discharge/charge profiles of Fe-MOF, Fe-MOF/RGO (5%) and Fe-MOF/
RGO (10%) at a current density of 500 mA g− 1. (f) Cycling performance and coulombic efficiency of Fe-MOF, Fe-MOF/RGO (5%) and Fe-MOF/RGO (10%) at a
current density of 500 mA g− 1. Reproduced ref. [77].

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Y. Jiang et al.
For instance, the first possible application of MOFs as an electrode for
LIBs was proposed by Li’s group in 2006 [68]. Subsequently, Combarieu
et al. [82] researched a novel composite hybrid material containing MIL-
53(Fe) with a 1:1 M ratio. The electrochemical capacity of MIL-53(Fe)
can be enhanced, by introducing this guest organic electroactive mole­
cule. The temperature-driven structural evolution of the MIL-53(Fe)
quinone1 phase is shown in Fig. 2a. But its capacity retention still was
not very good because of the progressive exchange between quinone and
DMC molecule. To further improve its performance. Then, Combelles
and his colleagues fully interpreted the redox mechanism of the MIL53
(Fe) by using a special calculation and analysis method [83]. The crystal
structure of the MIL53(Fe) is shown in Fig. 2b. Besides, this MIL53(Fe)
had been tested and is feasible as a cathode material for LIBs. This will
make LIBs have good rate performance. Although a specific capacity of
70 mAh g− 1 is very low, this is the first time that reversible Li insertion
has been observed in the MOFs system [84]. Electronic structure
calculation provides a special method to explain the ground state of Fe-
MOFs and its reactivity towards elemental lithium. In addition, Fe3+/
Fe2+ redox has a positive effect on electrochemical activation. In 2015,
Shin’s group [85] reported that the MIL-101(Fe) was used as an elec­
trode material for LIBs for the first time. The Fe3+/Fe2+ redox pair is
very active. However, it is not perfectly reversible in a lot of cycles.
Thus, to enhance the invertibility of the Fe2+/Fe3+ redox reaction, the
MIL-101(Fe) SBUs can be properly functionalized. When used as cathode
material, the Fe-based MOFs can show excellent electrochemical
performance.
Except cathode materials, the iron-based MOFs can be used as anode
materials. In 2017, Shen’s group [86] designed an organic material,
namely MIL-88B, as an anode material. This MIL-88B has a polyhedral
nanorod structure (Fig. 2c, d). When used as electrode material, it can
better promote the lithiation/de-lithiation behaviors of organic small
molecules. It had been found that the metal cluster was beneficial to
increase the reversible capacity. Test results showed that the initial
discharge/charge capacity was 1,603.3/819.2 mAh g− 1 at 100 mA g− 1.
When the MIL-88B electrode was tested at 60 mA g− 1, the reversible
capacity of MIL-88B could maintain about 744 mAh g− 1 over 400 cycles.
Therefore, the nanostructured MOFs are more suitable than other ma­
terials for stable charging and discharging processes. Even, the con­
ductivity and cycling performance of nanostructured MOFs were also
improved.
Composites are a synergistic combination of two or more materials,
which exhibit different overall properties as compared to the individual
species [87]. MOFs are highly porous materials constructed by inorganic
metal nodes and organic ligands, and have been extensively explored in
LIBs. Benefiting from their adjustable porous structures and controllable
compositions at molecular level, they can become advanced electrode
materials for LIBs [84,85]. However, Most MOFs do not have significant
conductivity, so some investigators hope to improve their conductivity
by introducing other conductive materials [77]. Among them, reduced
graphene oxide (RGO) with outstanding electrical conductivity becomes
a good composition material, which can enhance the conductivity of
MOFs via introducing them. Moreover, graphene also possesses an
adjustable porous structure, which can amortize the volume variation to
efficiently reduce the pulverization of active substances and increase the
cycling stability of MOFs [88]. For example, Jin et al. [77] obtained a Fe-
MOF/RGO composite as an anode material in LIBs. This Fe-MOF/RGO
(5%) composite has remarkable lithium storage performance and rate
performance (Fig. 2e, f). Therefore, the reversible capacity of Fe-MOF/
RGO (5%) composite reached 2,259.3 mAh g− 1 at 500 mA g− 1. Even,
the reversible capacity of Fe-MOF/RGO (5%) composite also achieved
1,010.3 mAh g− 1 over 200 cycles. In addition, the synergy of MOFs and
RGO can enhance the specific capacity of these batteries. Moreover,
graphene is only one of the carbon nanomaterials. Carbon nanomaterials
often are used as conductive agents to enhance the conductivity of other
materials. Therefore, Eftekhari et al. reported a LiFePO4/C nano­
composite as an anode [53]. The discharge capacity of the
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Electrochemistry Communications 122 (2021) 106881
nanocomposite attained 170 mAh g− 1 at 0.5C. But this nanocomposite as
electrodes can also become a supercapacitor at high capacitance rates. It
is a good method to increase the conductivity and cycling stability via
combining MOFs with carbon nanomaterials. In addition to carbon
nanomaterials, there are many other conductive materials that can be
researched.
Fe-based MOFs can show an enhanced electrochemical reactivity and
an excellent electrochemical property as electrode materials for LIBs.
Because of the oxidation of Fe2+ to Fe3+, Li ions can be inserted into the
structure of these Fe-based MOFs. However, compared with some
inorganic materials (e.g., Ag, Cu, and Au), the conductivity of Fe-based
MOFs is not good. And the poor conductivity of Fe-based MOFs will
hinder its practical application and lead to poor cycling performance of
LIBs.
3.1.2. Co-MOFs and their composites as electrode materials
In addition to Fe-MOFs as electrode materials in LIBs, Co-MOFs can
also be used as electrode materials for LIBs [89–94]. In 2009, Combarieu
et al. [95] have done pioneering work by using MOFs as the electrode
materials for LIBs. They discovered the first cathode material MIL-53
(Fe), and the MIL-53(Fe) had the capacity of 75 mAh g− 1. Subse­
quently, Co-MOFs are proven to possess good electrochemical perfor­
mance in LIBs due to their porosity and high specific area. Therefore, Co-
MOFs and their composites are widely used as electrode material in LIBs.
As the researchers further explore, Co-based MOFs are used as
electrode materials for LIBs. For instance, Gou’s group [89] obtained a
new material called Co2(OH)2BDC as an anode material by using a sol­
vothermal method in 2014. Test results showed that the Co2(OH)2BDC
showed an excellent cycling stability, and it maintained a good capacity
of 650 mAh g− 1 at 50 mA g− 1 over 100 cycles. Because terephthalic acid
(H2BDC), with carboxylate functional groups as nucleation sites, has
constructed many MOFs architectures, the 1,4-benzenedicarboxylic acid
could offer affluent candidates for continuous development [95,96].
Therefore, Hu et al. [90] acquired a Co-BDC MOF via a one-pot method
in 2016. When this MOF was used as anode material, test results dis­
played that it exhibited an outstanding discharge capacity of 1,090 mAh
g− 1 at 200 mA g− 1. As the current increases to 1,000 mA g− 1, the Co-BDC
MOF still showed the capacity of 611 mAh g− 1. During lithiation/de-
lithiation processes, cobalt will stay at Co2+ state. Hence, Li+ may be
directly intercalated into the organic part (e.g., benzene ring, carbox­
ylate moieties) without cobalt ions participation (Fig. 3f). This lithium
storage mechanism can effectively increase lithium storage capacity.
Even, this lithium storage mechanism will be a more effective method to
promote the development of MOFs-based active materials.
In 2016, some researchers had adopted this lithium storage mecha­
nism. For example, Li et al [91]. got a Co-BTC coordination polymer,
namely Co-BTC CPs, through using a common hydrothermal method.
They chose three different reaction solvents to generate CPs with sundry
sizes and morphologies. When these materials were used as electrode
materials, test results displayed that the cycling performance of three
different polymers was no outstanding different at 100 mA g− 1 (Fig. 3g).
However, when the current at 2 A g− 1, the distinction of reversible ca­
pacity was very visible (Fig. 3h). And the optimized product (CoBTC-
EtOH) showed an excellent reversible capacity of 473 mAh g− 1 at 2 A
g− 1 over 500 cycles and retained significant coulombic efficiency (about
100%). Even, their simple way can be extended to different types of
energy storage devices. Subsequently, they also used this mechanism to
research other MOFs. They obtained a new material called S-Co-MOF
with shell-like via using an uncomplicated surfactant-assisted sol­
vothermal approach [92]. The S-Co-MOF has two different kinds of
CoO6 octahedra. During electrochemical process, Li-ion was inserted
into the carboxyl group and benzene ring of the S-Co-MOF, accompanied
by the deformation of CoO6 octahedral sites. Test results showed a high
cycling stability of this MOF. The MOFs employed this mechanism to
show good initial coulombic efficiency and rate capability. Some re­
searchers have also studied the MOFs of other organic ligands. In 2017,
Y. Jiang et al. Electrochemistry Communications 122 (2021) 106881

Fig. 3. (a, b, c) Panoramic SEM micrographs of the as-synthesized CoCGr-2, CoCGr-10, and CoCGr-5, respectively. (d) Magnified SEM micrograph of the as-
synthesized CoCGr-5. Reproduced ref. [78]. (e) Schematic diagram of CoCOP nanowires. Reproduced ref. [94]. (f) Possible lithiation/delithiation sites for coordi­
nation with Li + in the organic moiety of Co-BDC MOF. Reproduced ref. [90]. (g) Cycling performances of CoBTC-EtOH, CoBTC-DMF, and CoBTC-DMF/EtOH at a
current density of 100 mA g− 1; (h) cycling performances of CoBTC-EtOH, CoBTC-DMF, and CoBTC-DMF/EtOH at a high current density of 2 A g− 1. Reproduced
ref. [91].

Liao et al. [93] obtained a new material-Co2(DOBDC) as an anode ma­
terial via a hydrothermal approach. When used as an anode, this MOFs
displayed a reversible capacity of 526.1 mAh g− 1 at 500 mA g− 1 over
200 charge/discharge cycles, with an excellent capacity of 408.2 mAh
g− 1 at 2 A g− 1. Moreover, the Co2(DOBDC) also kept high rate capability
due to its unique micro/nano-sized porous structure and sufficient
specific surface area.
Song et al. [94] obtained a one-dimensional cobalt coordination
polymer (CoCOP) nanowire through an easy hydrothermal method. Li-
ion transport in lithiation/de-lithiation processes is shown in Fig. 3e.
By this process, the CoCOP nanowire exhibited a capacity of 1,100 mAh
g− 1 at 20 mA g− 1. In addition, it also showed excellent high cycling
stability for over 1,000 cycles. 1D nanostructure can effectively provide
rapid electron and ion transport, while flexible nanowires or nanotubes
help to obtain stable structural integrity in various electrode configu­
rations [94]. Therefore, 1D MOF nanostructure is a good material to
improve lithium storage capacity. This points out a clear direction for
the future development of MOF.
Benefiting from the attractive features of Co-MOF, such as versatility,
tunability, and functionality, it can show an excellent reversible capacity
and retain significant coulombic efficiency [91,92]. However, these
MOFs similarly have some issues (e.g., poor conductivity, the expan­
sion/contraction of electrodes). In order to solve these problems of
MOFs, many investigators researched their composites as electrode for
LIBs [78,97]. These composites are obtained by combining with gra­
phene. Graphene possesses outstanding conductivity and layered
structure, which can effectively prevent the volume expansion of the
electrode. For example, In 2017, Li and co-workers synthesized a
Co2(OH)2BDC/carboxyl graphene (CGr) composite via using a simple in-
situ solvothermal method [78]. The morphology of this composite dis­
played layers and flakes by the SEM micrographs (Fig. 3a-d). And the
optimized composite (CoCGr-5) can attain an excellent reversible ca­
pacity of 1,368 mAh g− 1 at 100 mA g− 1. Moreover, it showed an
outstanding rate capability and a high cycling ability (818 mAh g− 1 at 1
A g− 1 over 400 cycles). This CoCGr-5 exhibited remarkable electro­
chemical performance because of the synergistic action between
Co2(OH)2BDC and CGr. Subsequently, Dong et al. [97] successfully
prepared two multi-functional MOF materials (i.e., Co(L) MOF, Cd(L)
MOF) via a plain and universal solvothermal method. The two multi-
function MOFs have the same coordination pattern. Subsequently,
MOFs/RGO hybrid material was synthesized via ball milling, and the
test results showed that this material demonstrated a good performance.
Even, compared with the above two multi-function MOFs, the perfor­
mance of this material is better. Therefore, this material and Co(L) MOF
were combined by Dong’s group. When the Co(L) MOF/RGO material
was used as an anode, the Co(L) MOF/RGO may show an outstanding
discharge capacity of 1,185 mAh g− 1 at the current density of 100 mA
g− 1 over 50 cycles. Here, they mainly investigated the impact of MOF
structural changes on performance. The electrochemical performance of
MOFs can be increased due to a special lithium ion insertion/extraction
mechanism.
Co-based MOFs similarly exhibit a good lithium storage capacity and
a remarkable cycle performance. Because the cobalt ions in the majority
of Co-based MOFs remain in the Co2+ state during charging/discharging
process. Thus, lithium ions can be inserted into the organic moieties of
Co-based MOFs without the change in the valence of cobalt ions during
the charge and discharge cycle. However, in some cobalt-based MOFs,
cobalt ions still exist to participate in the intercalation/deintercalation
of lithium ions. This may lead to an inefficient organic-moiety-
dominated lithium ions intercalation/deintercalation mechanism.

6
Y. Jiang et al.
3.1.3. Mn-MOFs and their composites as electrode materials
In addition to the above two types of MOFs, many investigators
began to look for other promising MOFs as electrode materials in LIBs.
Mn-based MOFs [98–100] are also electrode materials. In 2013, Liu’s
group [98] synthesized a 2D[Mn-(tfbdc) (4,4′ -bpy)(H2O)2] (Mn-LCP)
through a special method. Here, this MOFs held a characteristic of the
2D metal coordination polymers (Fig. 4a). And the initial discharge
capacity of the Mn − LCP electrode is very high. However, its capacity
decays rapidly at the second cycle (Fig. 4g). Even, in the fourth cycle, the
Mn-LCP displayed a reversible capacity of approximately 390 mAh g− 1.
Hence, the Mn-LCP as an electrode material still does not have too high
lithium storage capacity. Therefore, Maiti and his colleagues want to
enhance lithium storage capacity by using different materials as elec­
trodes. They successfully obtained a novel material-Mn-1,3,5-
benzenetricarboxylate MOF (Mn-BTC MOF) via a common sol­
vothermal method [99]. It was used as an anode material for the first
time. And the electron microscope images of the Mn-BTC MOF are
shown in Fig. 4c-f. The organic part of Mn-BTC MOF may affect lithium
ion insertion/extraction mechanism. Besides, the MOF may retain
extremely significant Li-storage ability via choosing a suitable organic
ligand. Therefore, this Mn-BTC MOF showed an excellent capacity of
694 mAh g− 1 at 0.1 A g− 1 and a brilliant cycling ability. In addition, the
three-dimensional structure of MOF can be stabilized due to the exis­
tence of π-π interaction. Finally, they also reported that the electro­
chemical performance may be further improved by grafting CNT into the
Mn-BTC MOF network. Subsequently, Zhang et al. [100] found a novel
electrochemical mechanism called the “bipolar charging” mechanism,
through analyzing the solid-state electrochemical process of a flexible
redox active MOF (Fig. 4b). The Mn-MOFs was used as a cathode ma­
terial for LIBs, and test results showed that the Mn-MOFs exhibit
remarkable cycle stability. Moreover, Li-ions and large volume anions
can be successfully inserted into the blowholes of the Mn-MOFs, helping
to improve its specific capacity. Even, these MOF materials are adopted
as universal electrode materials for different types of battery architec­
tures. This novel MOFs with enhanced discharge voltage and high en­
ergy density may be achieved via using different valence metal ions or
organic ligands. Finally, the MOF-based electronic storage materials
with excellent capacity, long life and good cycling performance can be
Fig. 4. (a) Two-dimensional layer structure of Mn − LCP. Reproduced ref. [98]. (b) Conceptual scheme underlying the new “Bipolar charging” chemistry. Repro­
duced ref. [100]. (c, d) FESEM micrographs and (e, f) TEM images of the synthesized Mn-BTC MOF at low and high magnifications. Reproduced ref. [99]. (g) Charge/
discharge profiles of the Mn − LCP electrode in a lithium-ion cell. (Inset) Discharge capacity vs cycle number from the second cycle. Reproduced ref. [98].
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expected to be achieved via combining the synthetic strategy with nano-
hybrid technology.
Benefiting from the porous structure of Mn-MOFs, Mn-MOFs can
show a good cycling performance and an excellent rate performance as
electrode material in LIBs. However, the conductivity of Mn-MOFs is not
excellent, resulting in poor reversible capacity and cycling performance.
Therefore, graphene with high conductivity has been found to be a very
promising anode material for LIBs. Simultaneously, the property of MOF
can be enhanced by combining with the graphene. Hence, He et al. [101]
also successfully synthesized a Mn-MOF/RGOn composite by using ter­
ephthalic acid non-covalent functionalized GO sheet as an effective
nucleation site and structure-directing template to guide the growth of
MOFs. Besides, the Mn-MOF/RGOn composite can be used as an anode
material, the obtained sample exhibited an excellent reversible capacity
and good rate performance as well as remarkable cycling performance.
Compared with the primitive Mn-MOF, the Mn-MOF/RGOn composite
was better. The conductivity and extensibility of the composite can be
enhanced, benefiting from the synergy of Mn-MOF and RGOn.
Mn-based MOFs can show an excellent rate performance and an
outstanding cycling stability. Even, the manganese cations can occur a
reversible valence change, and manganese cations also show higher Li
ions uptake ability. More important, Mn is an abundant element with
low environmental impact. However, the conductivity of Mn-based
MOFs still is poor, resulting in the low reversible capacity of Mn-based
MOFs in LIBs. Besides, the thermal stability of Mn-based MOF simi­
larly is not good. These problems need to be solved by a suitable method.
3.1.4. Cu-MOFs as electrode materials
In recent years, Cu-based MOFs [102–104] can also be used as po­
tential electrode materials. First, Zhang and his colleagues prepared a
new MOF material called Cu(2,7-AQDC) as a cathode material by
employing a facile synthetic strategy [102]. The schematic diagram of
the lattice structure of this Cu(2,7-AQDC) is shown in Fig. 5a. When the
battery is discharged, the redox activity of anthraquinone groups and
metal clusters is reversible. Besides, the ligand sites and metal cluster
nodes of the Cu(2,7-AQDC) can also display independent redox activity.
This is also the first instance of the porous materials with this charac­
teristic. These discoveries showed that the MOFs with good application
Y. Jiang et al.
potential for commercial batteries can be exploited through introducing
good manufacturing technologies such as the nanocrystals and the thin
films. Even, novel MOFs with high surface areas and higher reduction
voltages may be obtained by relating other three-dimensional transition
metals (e.g., Mn, Fe, and Co), which could extensively enhance the
electrochemical performance of the MOF-based batteries. In 2016, Maiti
and his colleagues also synthesized a new material-Cu-1,3,5-benzenet-
ricarboxylate MOF called Cu3(BTC)2 MOF through using a common
solvothermal approach, and they even explored the electrochemical
properties of this MOFs [103]. The morphological characteristics of the
Cu3(BTC)2 MOF are highlighted via the formation of soft clusters of
different truncated octahedral shaped crystal (Fig. 5b-e). When the
Cu3(BTC)2 MOF was used as an anode material for LIBs, test results
showed that this Cu3(BTC)2 MOF may exhibit a remarkable capacity
(740 mAh g− 1 at 96 mA g− 1) along with good cycling stability. Even, at
the current density of 383 mA g− 1, the Cu3(BTC)2 MOF also received an
outstanding specific capacity of 474 mAh g− 1, without palpable fading
up to 50 cycles. In addition, its charge storage mechanism may contain
redox participation of the carboxylate ligands. The redox active organic
ligands are introduced into porous MOF structure, which can improve
capacity. In the same year, Peng et al [104]. synthesized a
triphenylamine-based MOF material, namely Cu-TCA, by reasonably
organizing two redox active building blocks. When the Cu-TCA was used
as an active cathode material for the first time in LIBs, the Cu-TCA
showed a long stable cycling performance, while it also exhibited a
remarkable rate capability.
Cu-based MOFs have abundant redox active constituents, which are
the Cu2+ ions located at the metal cluster sites. And the redox change
between Cu2+ and Cu+ took place. Besides, Cu-based MOFs have many
very stable organic ligands. Therefore, Cu-based MOFs can show a good
cycling performance. Nevertheless, the capacity loss will firstly occur
around the metal cluster (Cu2+/Cu+), probably due to the unfinished
redox reaction on the copper ions and the structural instability of the
whole system.
3.1.5. Ni-MOFs and their composites as electrode materials
In addition, some researchers also considered Ni-based MOFs
[105,106] can be used as electrode materials for LIBs. In 2015, Zhang’s
group [106] gained a Ni-based MOF via using a one-pot hydrothermal
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Electrochemistry Communications 122 (2021) 106881
Fig. 5. (a) Top view of Kagome lattice type structure
of 1 and an indication figure of glided adjacent layers.
The metal cluster junctions were Cu2(Ac)4 paddle­
wheels. Reproduced ref. [102]. (b) FESEM micro­
graph, (c) & (d) high and low magnification TEM
images of the synthesized Cu3(BTC)2 MOF and (e)
FESEM micrpgraph of Cu3(BTC)2 MOF after 50
continuous cycles. Reproduced ref. [103]. (f) Charge/
discharge voltage profiles at a current density of 50
mA g− 1; (g) specific capacity and coulombic efficiency
versus cycle number. Reproduced ref. [105].
route. The Ni-based MOF had many evident ion pervasion channels. The
Ni-based MOF can be used as an anode active material in LIBs, test re­
sults showed that this Ni-based MOF can exhibit a reversible specific
capacity (620 mAh g− 1 at 100 mA g− 1 after 100 cycles) and maintain
approximate 100% coulombic efficiency. Besides, the Ni-based MOF
exhibited remarkable rate performance. In the same year, An and co-
workers obtained a novel material Ni-based MOF (called Ni–Me4bpz)
via using a simple solvothermal method [105]. The H2Me4bpz ligands
had flexible rotation characteristic and structural stability. And the
Ni–Me4bpz can offer two-dimensional layered structure due to the azo
metal salt coordination mode. Moreover, the flexible ligands and 2D
layered structure can enhance the lithium ion insertion/extraction and
the electrochemical stability of Ni–Me4bpz. Test results displayed that
this Ni–Me4bpz showed good specific capacity and excellent cycling
performance (Fig. 5f, g). Thus, Ni-based MOF materials can become
hope electrodes for battery devices.
Ni-MOFs similarly possess some outstanding features, such as pre­
venting huge volume change, improving ion transport kinetics, ect.
Thus, Ni-MOFs can obtain an excellent cycling performance. However,
Ni-MOF still exists a series of natural drawbacks, (e.g., poor thermal
stability and low discharge/charge potential). Benefiting from their high
theoretical capacity and reasonable discharge/charge potential, the
black phosphorus (BP) and CNT can become a very promising anode
material for LIBs [107,108]. On the other hand, BP is the thermody­
namically most stable allotrope and insoluble in most solvents [109].
Moreover, the layered structure of BP is good for ion transport. Thus, Ni-
MOF composite can become a good electrode material for LIBs by
combining with BP or CNT. Jin and co-workers successfully prepared a
2D NiCo-MOF in combination with BP [81]. The composite showed a
specific capacity of 853 mAh g− 1 at 0.5 A g− 1 and an excellent cycle
performance of 398 mAh g− 1 at 5 A g− 1 after 1,000 cycles. In addition,
Gou’s group [79] synthesized a [Ni3(HCOO)6]/CNTs micron ellipsoid
particles by tuning the reaction time and the regent concentration, in
which CNTs penetrate the entire particles thoroughly. The electro­
chemical activity of [Ni3(HCOO)6]/CNTs composite was much better
than that of the as-synthesized primitive [Ni3(HCOO)6]. This composite
can maintain good performance because of the efficient three-
dimensional conductive network formed by CNT. And the CNTs not
only bridged particles in between but also penetrated in the ellipsoid
Y. Jiang et al.
particles. This offers an effectively synthetic strategy to compound
conductive MOFs/CNTs composites.
Ni-based MOFs can provide large surface area and abundant pores
for Li+ intercalation, which can improve its charge capacity. Further­
more, the organic ligands linked to nickel ions allow for excellent
structural flexibility and stability, resulting in improved cycling per­
formance. However, its conductivity and thermal stability still are not
good. Even, its discharge/charge potential is also very high. Besides, the
structure changes during lithiation/de-lithiation cycle can lead to the
pulverization of the 3D rigid frameworks of Ni-based MOFs. These issues
lead to the poor cyclic stability of Ni-based MOFs as electrode materials
for LIBs.
3.1.6. Others MOFs and their composites as electrode materials
In order to search more different types of MOFs as electrode mate­
rials for LIBs, some researchers also study Zn-based MOFs. For example,
Li’s group [68] synthesized MOF-177 [Zn4O (1,3,5-benzenetricarboxylic
acid)] with a polycrystalline structure by using a common solvothermal
route, and studied its lithium storage behavior. Test results displayed
that the capacity of MOF-177 quickly declined from 400 mAh g− 1 to 105
mAh g− 1, which is only completed two charge and discharge cycles. The
reason of poor cycling ability is that the MOF-177 electrode undergoing
a conversion reaction with lithium during the cycle of cell:
Zn4 O(BTB)2 ⋅(DEF)m (H2 O)n + e− + Li+ →Zn + Li2 O (4)
The reaction (4) is irreversible, and the formed Li2O triggers the
structural collapse of MOF-177 during cycling (Fig. 6e, f). Therefore,
MOF-177 is not an ideal electrode material for LIBs. Subsequently, Lin
and his colleagues synthesized functionalized MOF (BMOF) with phenyl
and amine functional groups [110]. The BMOF can be used as an anode
active material. After testing, the BMOF exhibited remarkable thermal
and chemical stability. When the BMOF discharges at 100 mA g− 1, the
discharge capacity of the BMOF was about 190 mAh g− 1 after 200 cy­
cles. Even, the Li-storage ability of cell can be further improved through
raising the number of active N-rich functionality and surface area or
pore volume. Furthermore, the functionalized MOF also has an
outstanding specific capacity and good coulombic efficiency (Fig. 6g).
This MOF with the functionality and the porosity is a very good elec­
trode material.
Kaveevivitchai et al. [111] prepared a vanadium-based MOF VIV(O)
(bdc) [MIL-47] via a reflux approach. The MIL-47 is isostructural with
the iron compound MIL-53(Fe) (Fig. 6a-c). The electrochemical reaction
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Electrochemistry Communications 122 (2021) 106881
with lithium of the synthesized microporous VIV(O)(bdc) was also
researched. The MIL-47 may be reversibly cycled in an electrochemical
battery with Li metal as the counter electrode at rates up to 10C with
excellent specific capacity. Li/V(O)(bdc) cell may show the capacity of
82 mAh g− 1 at C/12 with about 100% coulombic efficiency. Compared
with the capacity of MIL-53(Fe), it is better. In addition, the electro­
chemical performance of this V-based MOF can be enhanced via further
studying of the mechanism between lithium insertion and modification
of the basic framework structure, such as the functionalization of
organic linking groups In 2016, Tian and co-workers synthesized two
types of new materials MOFs (called Co-MOF, Cd-MOF) as cathodes for
LIBs via controlling the diversification of anion and thermodynamic
[112]. These two types of MOFs have different sizes of porosity. And two
kinds of Cd(II) MOFs (MOFs 1 and MOFs 2) with one-dimensional non-
porous network and porous, non-interpenetrated two-dimensional
square grid architecture may be obtained, by using a simple complexing
method (Fig. 6d). Test results showed that two different kinds of Cd(II)
MOFs exhibited a superb specific capacity and a stable cycling perfor­
mance. Even, compared with the other two kinds of Co(II) MOFs (MOFs
3 and MOFs 4), they are also better. Moreover, the porosity and metal
nodes may also influence the electrochemical properties. Therefore, the
two-dimensional MOF 2 maintained the large porosity, and it showed a
much higher Li-ion diffusion coefficient (DLi) value than the one-
dimensional MOF 1. But these MOFs also have a disadvantage that is
the limited number of lithium atoms inserted in each formula unit, so
researchers need to adopt appropriate methods to enhance the perfor­
mance of these materials and increase the lithium-ion storage capacity.
Benefiting from their high specific surface area and porous structure,
these metal-based MOFs can exhibit excellent capacity and good cycling
ability. But the conductivity of these metal-based MOFs is poor. Hence, a
lot of investigators hope to modify the properties of these materials by
incorporating some conductive agent. In 2012, Zheng’s group [113]
synthesized a new shell/core nanocomposite called ZTO/ZIF-8 by using
the ZIF-8 to coat Zn2SnO4 (ZTO) nanoparticles. When this ZTO/ZIF-8
nanocomposite was used as an anode material, test results displayed
that it exhibited superb charging specific capacity and excellent cycling
performance. It also showed meaningfully improved cycling stability for
lithium ion intercalation. Even, the conductivity of ZTO/ZIF-8 nano­
composite proved to be much better than that of ZIF-8. These may be
attributed to the fact that the nanopore ZIF-8 on the electrode is bene­
ficial to release the stress caused by the rapid expansion of the volume
during Li-Sn alloying/dealloying process. This demonstrates that the
Fig. 6. Structure of VIV(O)(bdc) framework: (a)
Chain of trans corner-sharing VO6 octahedra. (b) VO6
chains cross-linked by 1,4-benzenedicarboxylate
(bdc). (c) Projection of the framework along the a-
axis showing one-dimensional diamond-shaped
channels. Reproduced ref. [111]. (d) Conceptual
schematic presentation of crystal engineering of
naphthalenediimide-based MOFs 1–4. Reproduced
ref. [112]. (e) Typical TEM images of the MOF-177
sample measured before electrochemical tests and
(f) examined after the first discharge process.
Reproduced ref. [68]. (g) Cycling performance and
coulombic efficiency of the electrodes made with
BMOF. Reproduced ref. [110].
Y. Jiang et al.
performance and the conductivity can be increased due to the ZIF-8 thin
layer. Subsequently, Han and his colleagues exploited a new MOF
sandwich coating approach called MOF-SC [114]. Test results showed
that the easily valid micro-Si treated with MOF-SC, namely C/Si/ZIF-8,
can achieve 1,700 uAh cm− 2 at 265 uA cm− 2. After 50 charge and
discharge cycles, it can also maintain 850 uAh cm− 2. Moreover, to
explored whether this approach is practical. Han’s group [114] prepared
different types of MOF materials, such as MOF-5, MIL-53, ZIF-67,
HKUST-1, and NH2-MIL-53, by using this approach. These MOF mate­
rials have different crystal structures. Because these MOF materials have
large surface areas and abundant gaps, the MOF layer is able to contain
more electrolytes and promote rapid lithium ion diffusion. Even, this can
decrease the overall impedance and further improve the rate perfor­
mance of the material. In addition, this special method can also be
successfully used in current commercial applications.
In 2020, Pourfarzad et al. [115] successfully prepared a Sn-based
reduced on Co-MOFs anode material by a solvothermal approach.
When using PEG400 polymeric surfactant, MOF1 was obtained with
trigonal (rhombohedral) structure, while MOF2 with monoclinic struc­
ture was got without the use of surfactants. The PEG400 polymeric
surfactant plays an important role to make MOF generate a special
structural order and a structural unit with trigonal network. Therefore,
MOF1 with trigonal structure exhibited a discharging capacity of about
615 mAh g− 1 in the first cycle, which was 634 mAh g− 1 in the second
cycle. However, the discharging capacity of MOF1 dropped to 400 mAh
g− 1 after 207 cycles. Compared with MOF2, the performance of MOF1
still is better. This idea can promote the design of new electrode mate­
rials with more reasonable nanostructures and better performance. In
the same year, Gao and his colleagues synthesized a novel SnO2@MOF/
graphene composite by a new and simple strategy [116]. This strategy is
good to incorporate SnO2 nanoparticles into Al-MOF according to the
optimal mass ratio, and then wrap the SnO2@MOF composite material
with graphene to prepare SnO2@MOF/graphene composite material.
This composite may offer abundant electroactive sites. And it also pro­
vided a special pathway to shorten ion transport because of its unique
structure and good electronic conductivity. In addition, the MOF pro­
tection layer can play an important role to enhance the lithium storage
of metal oxide-based anodes. This composite showed an outstanding
cycling stability with the specific capacity of about 450 mAh g− 1 over
1,000 cycles at 1,000 mA g− 1 and a good rate capability. Hence, this
approach provides a promising path for bimetallic nanostructure MOFs
as electrode materials in LIBs.
In addition to Fe-MOF, Co-MOF, Ni-MOF, Cu-MOF, Mn-MOF, some
other metal MOFs also show a good reversible discharge–charge ca­
pacity and an outstanding cycle performance. They have abundant pores
and many redox reactive metal ions, which can promote Li ions inter­
calation. However, their conductivity similarly is not outstanding. Thus,
they need to enhance conductivity by some easy methods, leading to the
improved electrochemical performance of LIBs.
3.2. MOF materials as solid-state electrolytes
Compared with traditional organic liquid electrolytes, solid-state
electrolytes (SSEs) have become a research hotspot in the last ten
years [117,118]. SSEs can successfully resolve a series of safety prob­
lems of organic liquid electrolyte [118]. There are three different types
of polymer SSEs [119], such as polyacrylonitrile (PAN), polyethylene
oxide (PEO), and polymethyl methacrylate (PMMA). Even, SSEs can
make good contact with the electrode interface. MOFs have many ad­
vantages with adjustability and porosity. Hence, MOFs can become
potential candidates as SSEs materials for LIBs, due to their large surface
area, micro or nano-sized pores, and thermal stability.
For example, Angulakshmi and his colleagues also prepared com­
posite polymer electrolyte through using a simple hot-press technology
in 2014 [120]. The composite polymer electrolyte is composed of the
PEO and the LiN(CF3SO2)2 (LiTFSI), and doped with magnesium-
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Electrochemistry Communications 122 (2021) 106881
benzene tricarboxylate MOF (Mg-BTC MOF). Test results showed that
the ionic conductivity of the polymer film can be improved by incor­
porating Mg-BTC MOF into the polymer matrix. In addition, its dura­
bility and elongation as well as thermal stability also are improved by
using the same method. Subsequently, Gerbaldi and his colleagues
successfully acquired a new Al-based MOF called Al-BTC MOF as SSEs
[121]. And the nanocomposite polymer electrolyte membrane can be
obtained by incorporating Al-BTC MOF into the polymer electrolyte.
After a lengthened storage time, this NCPE membrane is still very stable
to Li metal. And it can show an excellent cycling performance even at
middle temperatures. Thus, this is beneficial to the development of high-
performance, safe solid LIBs. But some interface problems may affect the
energy density of the cell. The solid electrolytes have now become an
important direction for the progress of solid LIBs. Therefore, Wang and
his colleagues discovered a novel kind of solid-like electrolyte (SLE)
[122]. It is mainly composed of MOF nanocrystals impregnated with
ionic liquid (Li-IL@MOF). It has remarkable electrochemical perfor­
mance and superb ionic conductivity as well as good lithium ion diffu­
sion effect. Even, it also has excellent compatibility. By changing the ion
species in the ionic liquid, this good idea can be applied to commercial
energy storage devices.
In 2019, Mathew and co-workers successfully prepared PEO based
composite polymer electrolyte via using a special strategy [123]. First,
they synthesized Mg-1,4-benzenedicarboxylic acid (Mg-TPA) and Mg-
1,3,5-benzene tricarboxylic acid (Mg-TMA) MOFs, and then they used
the PEO matrix to wrap the LiTFSI as salt and the Mg-TPA or the Mg-
TMA. This polymer electrolyte had a good ionic conductivity. The
polymer electrolyte with incorporation Mg-TPA may provide the highest
ionic conductivity, because its low surface charge can accelerate the
transfer of Li-ions in the composite polymer electrolyte. In addition, this
polymer electrolyte with incorporation MOF can better contact with the
lithium metal anode. Subsequently, Angulakshmi’s group successfully
obtained PEO-based composite polymer electrolyte through using a
simple hot press approach [80]. This polymer electrolyte was synthe­
sized by incorporating the amine-functionalized, Zr-based MOF @silica
(UiO-66-NH2@SiO2) and the LiTFSI. The polymer electrolyte with
incorporation UiO-66-NH2@SiO2 can gain an outstanding ionic con­
ductivity and provide a better compatibility, even it can significantly
inhibit the formation and growth of lithium dendrites. It also exhibited a
discharge capacity of 151 mAh g− 1 at 0.1C at 60 ℃. Due to the more
uniform ion conduction cavity and channel in the PEO matrix, it can
have enhanced electrochemical properties. This polymer electrolyte can
also enhance electrode − solid electrolyte interfacial property. Hence,
the superb polymer electrolytes can be obtained by incorporating these
nanostructure MOFs into electrolytes.
In summary, the MOF electrode materials can provide good lithium
ion storage and outstanding cycling ability, due to their excellent
functions, such as thermal stability, adjustable nanostructure, and me­
chanical flexibility. Despite great progress, the MOFs still exist many
shortages (e.g. the low conductivity, insulation, and inferior electro­
chemical stability). These deficiencies lead to LIBs not maintain much
better electrochemical performance. Hence, solving these problems is
the top priority of the further progress of LIBs. As the electrode materials
or SSEs, the MOFs and their composites have both advantages and
limitations to the whole battery systems. In the future, researchers need
to further design MOFs with better functionality.
3.3. MOF derivatives as electrode materials
MOFs are used as good electrode materials, and their derivatives can
also be used as excellent electrode materials in LIBs [124]. Its derivatives
mainly include metal oxides and porous carbon materials [125,126].
Metal oxides are considered as promising anode materials to effectively
replace graphite in LIBs, due to their low-cost, plentiful resources, and
higher reversible specific capacities [127]. However, traditional metal
oxides as anode materials usually have the problems of poor rate
Y. Jiang et al.
performance and capacity retention. Apparently, new metal oxides
(especially their controllable morphology and adjustable size) need to
be developed. Thus, MOFs stood out from more materials. Different
kinds of metal oxides can be obtained via annealing MOFs in air. This
can get different types of metal oxides, which largely depends on the
types of inherent structures and metal ions/clusters. Porous carbon
materials are also one of the most promising alternatives to graphite
materials [128]. Porous carbon materials can show an outstanding cycle
performance in LIBs, mainly because the porous structures can promote
Li+ intercalation/de-intercalation and buffer the volume change and
impact during charging and discharging process. Various porous carbon
materials can be obtained by pyrolyzing MOFs in the argon/nitrogen
atmosphere.
MOFs-derived metal oxides can play a significant role as anode
materials in rechargeable secondary batteries, particularly LIBs. Metal
oxides can be obtained by using MOFs as precursors or self-sacrificing
templates. For example, Xu and his co-workers synthesized Co3O4
nanoparticles by calcining Co-MOF [Co3(NDC)3(DMF)4] at 600 ◦ C for 1
h in air atmosphere [129]. They gained Co3O4 nanoparticles with the
diameter of about 250 nm composed of the small nanoparticles with the
size of about 25 nm. However, these Co3O4 nanoparticles were
agglomerated. Despite, this material also showed a good reversible ca­
pacity of 965 mAh g− 1, but its cycling stability and rate performance are
poor. Subsequently, Han et al. successfully prepared a porous hollow
Co3O4 parallelepiped by calcining Co-MOF ([Co3(HCOO)6]⋅DMF) in two
steps in air [130]. This material showed an enhanced reversible capac­
ity, an excellent cyclic stability (1,115 mAh g− 1 at 100 mA g− 1 after 50
cycles) and a remarkable rate capability. This material can display
outstanding electrochemical performance due to its unique nano­
structure (porous hollow structure), which facilitates Li+ intercalation/
de-intercalation and reliefs the volume change and impact during
charging and discharging process. In 2018, Li’ group successfully gained
porous Co3O4 nanosheets as anode materials by calcining the CoBDC
precursor in air atmosphere [131]. The porous Co3O4 nanosheets
exhibited a unique structure with wrinkle layer, which is assembled
from uniform Co3O4 nanoparticles. Because of the unique structure of
the material, it as anode material can show a good specific capacity of
1,477 mAh g− 1 at 100 mA g− 1 after 160 cycles and 775 mAh g− 1 at 1 A
g− 1 after 200 cycles. More importantly, its rate performance also was
greatly improved, with a capacity of 580 mAh g− 1 at 10 A g− 1. Thus,
metal oxides with the unique structure can be better electrode materials
in LIBs.
Except derived for being transformed into metal oxide, MOFs can
also be derived converted into porous carbon materials (carbon and
carbon based materials). For instance, Zhuang and his co-workers re­
ported a highly dispersed supported Co3O4 on N-doped porous carbon
(NPC) [132]. This material was obtained by annealing ZIF-67/COF at
500 ◦ C for 2 h with a heating rate of 5 ◦ C min− 1. This material as elec­
trode material can show a reversible capacity of 785 mAh g− 1 at 500 mA
g− 1, along with a 99.65% Coulombic efficiency, benefiting from its large
specific surface area. Not long after this, Huang’ s group successfully
synthesized a new hybrid hollow porous ZnO/C nanocages by calcining
MOF-5 at 500◦ C for 2 h with a heating rate of 5◦ C min− 1 in nitrogen
atmosphere [133]. The as-prepared ZnO nanoparticles obtain enhanced
conductivity, due to a layer of uniformly carbon layer. In addition, the
material displayed a high specific capacity (750 mAh g− 1 at 100 mA g− 1)
and an excellent remarkable rate performance (351 mAh g− 1 at 2,000
mA g− 1). Mainly because its hollow structure can adapt the volume
change and impact during charging and discharging process and its
conductivity is also good. Recently, Liu et al. reported a MOF-derived 3D
hollow porous carbon/graphene composite (HPCGC) via annealing ZIF-
8/graphene oxide at 800 ◦ C for 2 h under nitrogen atmosphere [134].
When the composite was used as electrode material, it can exhibit a
specific capacity of 403.1 mAh g− 1 at 5 A g− 1 after 1000 cycles and a
superior rate stability during long-time cycling. Benefiting from its large
surface area and unique structure, the adsorption/desorption of Li+ will
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Electrochemistry Communications 122 (2021) 106881
be improved.
In summary, in addition to the materials mentioned above, there are
many different kinds of metal-based MOFs (e.g., Fe-MOF [136–138], Ni-
MOF [139,140], Mn-MOF [141–143], etc.) (Table 1). They can also be
transformed into metal oxides and porous carbon materials. These de­
rivatives can also show an excellent electrochemical performance. Their
derivatives obtain large surface area and unique structure, which can
help to improve Li ions intercalation/de-intercalation in LIBs.
4. Application of MOF materials in Li-S batteries
Over the past ten years, Li-S batteries have high-theoretical energy
density (about 2,600 Wh kg− 1). Compared with LIBs, Li-S batteries are
better. Even, Li-S batteries also possess high theoretical capacity and
natural abundance [60,158]. Because the sulfur resources on the earth
are very rich. The elemental sulfur also has a lot of superiorities. How­
ever, during the charge and discharge cycle, some sulfides will limit the
performance of Li-S batteries, and the most dominant problem is the
“shuttle effect” of polysulfides [159]. MOFs can slow down this effect
well due to their advantages, such as outstanding extensibility and
adjustable structure. Hence, a lot of investigators have tried to use MOFs
(Table 4) as host materials to limit polysulfide formation.
4.1. MOFs and their composites as host materials
Despite MOFs and their composites as host materials still can’t be
used for commercial application of large-area Li-S batteries. Many in­
vestigators hope that Li-S batteries can obtain excellent cell character­
istics. With further deep investigation on nanostructure MOFs, they
found that the surface area and voids of MOFs can even be improved,
which makes MOFs important host materials for Li-S batteries. Thus,
MOFs and their composites are able to be used as hopeful cathode ma­
terials in Li-S batteries systems [160–166]. In 2011, Demir-Cakan and
co-workers reported a new MOF material called MIL-100(Cr) as an
electrode material in Li-S batteries [160]. After the sulfur-containing
electrode is immersed in the hole of the MOF, it can excellently keep
the capacity not to drop. In addition, the insulated medium hole MIL-
100 (Cr) can promote the normal charging and discharging of Li-S bat­
teries. Compared with the mesoporous carbon, it is also better. This
demonstrates that it is more important to limit the polysulfide shuttle.
And it can exhibit remarkable electrochemical performance because of
the advantages of MIL-100(Cr), such as the structural adjustability and
mechanical flexibility. This strategy can be further applied in other
similar structures.
In 2014, Zhou et al. [161] reported a ZIF-8 nanocrystal as a sulfur
cathode material (Fig. 7a). When charging and discharging cycle
(Fig. 7b), the ZIF-8 nanocrystal showed stable cycling performance.
When 30 wt% sulfur is added to the cathode, it may exhibit good specific
capacity of 1,055 mAh g− 1 at 0.1C and 710 mAh g− 1 at 1C. The atten­
uation of capacity was 0.08% per cycle at 0.5C more than 300 cycles.
Even, compared with three other different MOFs, i.e., HKUST-1, MIL-53
(Al), and NH2-MIL-53 (Al), the ZIF-8 can show better in long-cycle. In
addition, the particle size of this material can affect the electrochemical
performance of Li-S batteries, because the small grain and pore of the
MOF host can make Li-S batteries attain an excellent capacity and stable
cycling performance. Subsequently, they successively prepared five
kinds of ZIF-8 samples with different particle sizes (from < 20 nm to
greater than 1 mm) [162]. When these materials were used as cathode
materials, test results displayed that the loss of ZIF-8 particle size will
enhance the utilization rate of sulfur. However, in the case of medium
size (the 200 nm of ZIF-8), the best cycle stability can be attained (up to
75% in 250 cycles at 0.5C). Therefore, finding out the “golden size”, for
the host material is very important.
Wang’s group [163] exploited a representative Zr-metalloporphyrin
framework called MOF-525 and the mixed-MOF approach, fabricating
novel sulfur host for Li-S batteries in 2015. The individual structure of
Y. Jiang et al. Electrochemistry Communications 122 (2021) 106881

Table 1
Summary of MOF derivatives for LIBs.
Electrode material MOF template Initial Coulombic Efficiency (%) Reversible Capacity (mAh g− 1) Refs.
− 1
Co3O4 Co3(NDC)3(DMF)4 75 40 at 80 mA g over 50 cycles [129]
Co3O4 [Co3(HCOO)6]⋅DMF 68 1,100 at 100 mA g− 1 over 50 cycles [130]
Co3O4 CoBDC 69.06 775 at 1,000 mA g− 1 over 200 cycles [131]
Co3O4/NPC ZIF-67/COF 72.9 782.76 at 500 mA g− 1 over 300 cycles [132]
Co3O4 Co–BTC 51 886 at 100 mA g− 1 over 100 cycles [135]
ZnO/C MOF-5 52.9 750 at 100 mA g− 1 over 100 cycles [133]
HPCGCs ZIF-8/ZGO – 403.1 at 5,000 mA g− 1 over 1,000 cycles [134]
LiFePO4 MIL-100(Fe) – – [136]
N-doped graphene/Fe–Fe3C MIL-100(Fe) 24.6 607 at 1,000 mA g− 1 over 100 cycles [137]
ZnO/ZnFe2O4/C FeIII -MOF-5 75.6 988 at 2,000 mA g− 1 over 100 cycles [138]
NiSb ⊂ CHS Ni-MOFs 53.8 309 at 1,000 mA g− 1 over 1,000 cycles [139]
NiO Ni-MOFs 72 1,019 at 100 mA g− 1 over 100 cycles [140]
MnOx Mn-MOF 71.3 1,217.7 at 200 mA g− 1 over 160 cycles [141]
MnO@C Mn-BTC 54.9 1,221 at 100 mA g− 1 over 100 cycles [142]
MnOx/C Mn-MOF 73 884 at 100 mA g− 1 over 100 cycles [143]
CuO/C [Cu3(btc)2]n 60 510.5 at 100 mA g− 1 over 200 cycles [144]
CuO/C Cu–BTC 75.3 505 at 100 mA g− 1 over 200 cycles [145]
SnO/C Sn–BDC 76 950 at 50 mA g− 1 over 100 cycles [146]
SnO2@C SnCl2@HKUST–1 57 880 at 100 mA g− 1 over 200 cycles [147]
Co3V2O8 Co–V–BDC 100 650 at 5,000 mA g− 1 over 400 cycles [148]
ZnO/NiO Zn–Ni–BDC 62.9 1, 008.6 at 100 mA g− 1 over 200 cycles [149]
TiO2 MIL–125(Ti) 86 122 at 1,680 mA g− 1 over 1,100 cycles [150]
α–Fe2O3 MIL–88B 69 1,338 at 100 mA g− 1 over 40 cycles [151]
In2O3/C MIL–68(In) 43 720 at 100 mA g− 1 over 150 cycles [152]
ZnO/CNF ZIF–8/PAN 65 818 at 100 mA g− 1 over 100 cycles [153]
ZnO/ZnFe2O4 Zn3[Fe(CN)6]2 63.8 804 at 1,000 mA g− 1 over 500 cycles [154]
ZnCo2O4/ZnO/C ZnCoCP 75.3 800 at 1,000 mA g− 1 over 400 cycles [155]
Co3O4/CoMoO4 PMo12O40@ZIF-67 65 750.6 at 100 mA g− 1 over 50 cycles [156]
CuO@C Cu–BTC 42.8 613 at 500 mA g− 1 over 700 cycles [157]

this material can enable a Cu2+ site to offer two Lewis acid sites,
permitting it to wrap more sulfur. The high porosity of this material can
absorb a lot of sulfur. When this material was used as a cathode material,
test results showed that it showed a superb performance with a good
reversible capacity (propinquity 700 mAh g− 1 at 0.5C after 200 cycles)
(Fig. 7e). In addition, the combination of special open Lewis acid metal
site and high porosity can make MOF-525(Cu) as the best MOF host for
the sulfur limitation. Subsequently, Li and his colleagues prepared a new
MOF material with open and semi-open channels [164]. This material is
used as the host to capture sulfur. Compared with a lot of the MOF/S
composites, the open channel of this material can assure a higher
loading quantitative of S (S content is 72 wt% for active material; 50.4
wt% for electrode). Those semi-open channels with aromatic ring
antennae ensure remarkable discharge capacity (1,092 mAh g− 1 at 0.1C)
and outstanding cycling stability. This method can also be further
applied to other porous materials.
In 2017, Shanthi et al. [165] synthesized a sulfur-containing non-
carbonized MOF called S-MOF. This material can be used as a cathode,
and the S-MOF cathode exhibited a capacity of 1,476 mAh g− 1 stabi­
lizing at about 609 mAh g− 1 with almost no attenuation over 200 cycles
(Fig. 7f). However, the capacity reduction was observed in the first 10
cycles due to the oxidation of some infiltrated sulfur. The appearance of
carbonate species in the MOF architecture leads to the formation of C-S
bond species, which causes polysulfides to remain on the electrode
surface. Moreover, the potential of nano-porous non-carbonized MOFs
as a host for sulfur also establishes the importance of chemical bond and
pore-driven shrinkage in stabilizing electrochemically active sulfur.
Subsequently, Liu et al. [166] synthesized a new manganese-based MOF
with cubic cages as an effective cathode host material. And these cubic
cage walls have a lot of open metal sites (OMS) gained from the 9-man­
ganese node. The manganese cluster-based MOF as cathode had good
electrochemical performance because of the synergetic effect. There­
fore, the manganese cluster-based MOF exhibited a remarkable initial
specific capacity of 1,460 mAh g− 1 at 0.2C and cycling stability with a
remaining capacity of ~ 990 mAh g− 1 at 0.2C after 200 cycles. In
addition, it also showed an approximate repeatable rate performance
because of a strong binding of soluble polysulfides. The activated MOF
can offer physical trapping and chemisorption to prevent polysulfide
shuttle, and can effectively impregnate sulfur to promote mass transfer.
In 2020, Benítez and his colleagues prepared MIL-88A, based on Fe
fumarate, via an easy and fast ultrasonic-assisted probe approach [167].
The synthesized MIL-88A molecule had a special shape. It possessed a
central prismatic part and pyramidal terminal part, which exactly dis­
played a double microporous-mesoporous MOF system. The SEM images
of MIL-88A are shown in Fig. 7c, d. The shape and size of the MIL-88A
molecules are very conducive to promoting dispersion and optimal
sulfur absorption. Even, The MIL-88A material showed the superb
crystallinity, large surface area, and high pore volume. Moreover, this
MIL-88A material was appropriate to be used as a matrix to host sulfur
for Li-S batteries. This type of materials with polyhedral and porous are
an effective cathode material for Li-S batteries.
The poor stability and electrical conductivity of MOFs is a crucial
factor that hinders them from attaining high electrochemical perfor­
mance. These can mainly lead to the low charge/discharge capacity of
Li-S batteries in an electrochemical process. Thus, a large number of
investigators have focused on using MOFs and other materials (e.g.,
graphene [168], CNT [169]) to make composites to reduce these
shortcomings. These materials usually are very high electrical conduc­
tivity. Besides, the unique structure of them similarly promotes Li-ions
intercalation/de-intercalation and slow down the volume change and
impact during charging and discharging process. Therefore, MOF com­
posites can be researched as an electrode to fix sulfur in Li-S batteries
[167,170]. Benítez’s group [167] synthesized a composite MIL-88A@S
via a typical melt diffusion approach at 155 ℃. This MIL-88A@S com­
posite maintained higher electrochemical performance than that of the
MIL-88A. When the MIL-88A@S was used as a cathode material for Li-S
batteries, it showed a stable specific capacity of more than 400 mAh g− 1
at 0.1C and cycle stability with a good reversible capacity of more than
300 mAh g− 1 at 0.5C over 1,000 cycles. Even, it also exhibited good
coulombic efficiency. Thus, this demonstrated that the MIL-88A@S
composite may be a hope electrode material for Li-S battery. In 2014,
Zhao and his colleagues reported a graphene/Cr-MOF (called MIL-101)
composite as a cathode host material to fix sulfur in Li-S batteries [170].
The MIL-101 had a much larger surface area (5,000 m2 g− 1) and pore

12
Y. Jiang et al.
Fig. 7. (a) Factors for consideration in the rational design of an efficient cathode made from MOF and sulfur. (b) Graphical model of the S/MOF system in the
discharge process. Reproduced ref. [161]. (c, d) SEM images at different magnifications for MIL-88A MOF. Reproduced ref. [167]. (e) Cycling performance of
S@MOF-525(Cu). Reproduced ref. [163]. (f) Cycling performance of S-Zn-MOF and commercial sulfur at 0.2C rate. Reproduced ref. [165].
volume (more than 1.6 m3 g− 1) than that of MIL-100 [160]. Sulfur is
highly dispersed into the pores with strong interaction due to the indi­
vidual pore structure and large surface area. Moreover, they also syn­
thesized a GNS-MIL-101(Cr)/S composite as a cathode via using a two-
step method (Fig. 8a). The graphene wrapped around this composite
material to build an excellent conducting network and a physical
container. Therefore, the electrochemical properties of this composite
were remarkably improved. When used as the sulfur cathode, the GNS-
MIL-101(Cr)/S composite showed an outstanding reversible capacity
(809 mAh g− 1 over 134 cycles) and an excellent coulombic efficiency
(96.6%) with capacity retention (95%) at 0.8C. However, there is a
problem of rapid decrease in capacity caused by dissolution of
polysulfide.
To solve this problem, Zheng and co-workers prepared a novel Ni-
based MOF (Ni-MOF) [36]. The crystal architecture of Ni-MOF is
shown in Fig. 8h. And the Ni-MOF can significantly fix the polysulfide in
the cathode structure by physical and chemical interaction at the mo­
lecular level. Moreover, the Ni-MOF/S composite had a good cycling
performance (Fig. 8i). Because it provides an ideal matrix to limit pol­
ysulfide and the interaction between polysulfides bases and Lewis acidic
Ni(II) centers, this remarkably slows down the rate of migration of sol­
uble polysulfides from the pores. Due to their outstanding internal
structure, high conductivity and good polysulfide chemisorption, the
carbon nanomaterials were also studied. In 2018, Pu et al. [34] prepared
a new University of Oslo-66 (UiO-66)/carbon nanotube (UC) composite
through a simple one-pot synthesis approach. Moreover, the flexible and
interlaced CNTs throughout mechanically stable UiO-66 nanoparticle
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Electrochemistry Communications 122 (2021) 106881
construct a reliable three-dimensional conductive network, enhancing
the flexibility of the host frameworks. Meanwhile, the introduction of
competitive collaboration will lead to many defects in the lack of linkers,
which greatly increases the number of active sites in the UiO-66
framework. When the UC composite was used as an active sulfur cath­
ode, it showed a good initial capacity (925 mAh g− 1 at 0.5 A g− 1) and
low capacity attenuation with the capacity decline of 0.071% each cycle
at 1 A g− 1 over 800 cycles.
In 2019, Cai’s group [168] successfully prepared a highly conductive
MOF called Ni3(HITP)2 as the sulfur host material through a facile
method. The SEM images of Ni3(HITP)2 of are shown in Fig. 8b-d.
Furthermore, they also used CNTs to replace the traditional conductive
additive acetylene black to build a matrix conductive network. Li-S
batteries will have an excellent cycling performance by this strategy.
When the sulfur content of S@Ni3(HITP)2 was 65.5 wt%, it exhibited a
good sulfur utilization and cycling durability. It showed an outstanding
initial capacity (1,302.9 mAh g− 1) and excellent capacity retention
(848.9 mAh g− 1) at 0.2C over 100 cycles. Even, at 1C, it also delivered a
high reversible discharge capacity of 629.6 mAh g− 1 over 300 cycles.
The SEM images of S@Ni3(HITP)2 are shown in Fig. 8e-g. Subsequently,
Wu et al. [169] obtained a 3D hierarchical structure MOFs-on-rGO
compartment as a sulfur host via a facile approach. This approach in­
cludes in situ reduced GO and combined MOFs. The MOF-on-rGO
compartment inherits the advantages of good conductivity, excellent
porosity, and high polarity. Hence, it may delay the diffusion and
transfer of soluble polysulfides. It showed a superb discharge capacity
(1,250 mAh g− 1 at 0.1C). At high rate of 1C, it also exhibited a good
Y. Jiang et al.
Fig. 8. (a) Schematic illustration of the GNS-MIL-101(Cr)/S composite preparation. Reproduced ref. [170]. (b-d) The SEM images of Ni3(HITP)2 and (e-g)
S@Ni3(HITP)2 at different scales. Reproduced ref. [168]. (h) Crystal structure of the Ni-MOF. (i) Cycling performance of Ni-MOF/S composite at 0.1 and 0.2C at
1.5–3.0 V. Reproduced ref. [36].
reversible capacity of 601 mAh g− 1 after 400 cycles. These methods
provide examples for some nanostructured MOFs as the sulfur host
cathode.
Benefit from their porous structure and high surface area, MOFs and
their composites are beneficial to the immobilization of polysulfides
when they are used as host materials. Therefore, these electrode mate­
rials can obtain remarkable electrochemical performance in Li-S batte­
ries. Nevertheless, they are also possible that the resistance of Li–S
batteries would raise due to the low speed of Li ions diffusion. Hence, the
utilization of sulfur may also step down. Hence, the appropriate unique
structure of the MOF materials needs to be further designed through a
suitable method.
4.2. MOF materials as functional separators
MOFs are also considered as potential candidate as ionic sieves for
selective modulation of ion transmission because of their nano-
structure, large surface area, and highly ordered porosity. Thus, MOF
composites have been widely studied as functional separators for Li-S
batteries. These functional separators can slow down a series of nega­
tive effects caused by the ‘shuttle effect’. For example, Bai’s group [171]
also synthesized a novel Zn(II)-based MOF@GO separator. And the Zn
(II)-based MOF@GO composite can solve this problem. The Zn(II)-
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Electrochemistry Communications 122 (2021) 106881
based MOF@GO composite can be used as a high-efficient ionic sieve,
allowing polysulfides to pass through the separator and transfer to the
anode. The schematic diagram of Zn(II)-based MOF@GO separator is
shown in Fig. 9a. In addition, this composite also displayed an
outstanding capacity of 1,005 mAh g− 1 at 0.5C and low capacity-fading
rate with the capacity attenuation of 0.041% each cycle at 1C over 1,000
cycles. Even, the electrochemical stability of this composite was also
very remarkable. Subsequently, Li and his colleagues exploited a light
and flexible bifunctional separator (B/2D MOF-Co) [172]. They used a
layer-by-layer method of assembling bacterial cellulose (BC) and 2D
ultra-thin MOF-Co. This bifunctional separator has many advantages,
such as adjusting the stripping of lithium, inhibiting the migration of
polysulfides, and adjusting the plating behavior because of the role of Co
single atom array on the surface of 2D MOF-Co nanosheets. When this
bifunctional separator was used by Li-S batteries, it exhibited a stable
cycling performance with an ultra-low capacity attenuation rate of
0.07% each cycle over 600 cycles. Even, at a high sulfur loading of 7.8
mg cm− 2, it still achieved an excellent reversible areal capacity (5.0 mAh
cm− 2) over 200 cycles.
Ma’s group [173] prepared a flexible MOF aerogel by growing MOF
nanoparticles (i.e. ZIF-8 and UiO-66) in situ on BC. The composite aer­
ogel inherits good porosity and outstanding flexibility from the raw
material MOF and BC templates, respectively. Therefore, the BC@ZIF-8
Y. Jiang et al.
composite aerogel sponge had lower density, good mass transfer effi­
ciency, high porosity, and brilliant heavy metal ion adsorption perfor­
mance. And the BC@UiO-66 flexible composite aerogel membrane
showed an outstanding specific capacity of 631 mAh g− 1 at 0.5C over
100 cycles of charging/discharging. The SEM image of the BC@UiO-66
material is shown in Fig. 9b. Even, the sample BC@UiO-66 was further
coated with polydopamine to dispute the non-conducting material from
transferring into the electrolyte. The SEM and TEM image of the
BC@UiO-66@PDA composite is shown in Fig. 9c, d. The BC@UiO-
66@PDA composite aerogel film exhibited an outstanding reversible
capacity of 739 mAh g− 1 at 0.5C over 100 cycles. Even, it maintained a
small capacity decay rate at 0.5C over 100 cycles. This also offers novel
ideas for the design and manufacture of multifunctional MOFs.
In 2020, Li et al. [174] prepared a hybrid membrane with ZIF-67
grown in situ on carbon nanofibers (CNFs) called ZIF/CNFs as an
interlayer. The ZIF/CNFs interlayer can slow down the dissolution and
transfer of polysulfides, and even can capture polysulfides for reuse,
because of the micropores of the ZIF nanoboxes and connected electron
transfer network constructed by CNFs. With this now ZIF/CNFs inter­
layer, Li-S batteries exhibited an excellent specific capacity of 1,334
mAh g− 1 at 1C and a good cycling performance. Besides, it showed an
outstanding capacity of 781 mAh g− 1 even at 2C. Subsequently, Zhou
and co-workers synthesized a double-layered MOF-PAN/rGO-PAN
nanofiber membrane [70]. This membrane has thermal stability, superb
mechanical property and high electrolyte absorption rate, even can
capture polysulfides. When the cell used this membrane, it showed an
outstanding initial capacity of 1,302 mAh g− 1 at 0.5C. Especially, at high
rate of 5C, the capacity decay rate of the cell was 0.03% each cycle after
600 cycles (Fig. 9e). Furthermore, the Li-S battery may provide a high
areal capacity at high sulfur loading over 50 cycles (Fig. 9f). From the
discussion above, MOF materials still have great development in the
application of functional separators.
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Electrochemistry Communications 122 (2021) 106881
4.3. MOF derivatives as host materials
MOFs can absorb a large amount of sulfur, owing to their high
porosity. But they can’t adequately utilize sulfur resources due to their
poor electrical conductivity. Thus, MOF-derived carbon and carbon­
–metal composite, which can be obtained by annealing MOFs, are good
options to be employed as sulfur host materials in Li-S batteries
[175,176]. They gain remarkable electrical conductivity to improve the
insulating nature of sulfur because of their uniform layers of carbon. And
they can effective sorption to prevent polysulfides from dissolution. In
addition, their high porosity also improves the load capacity of sulfur.
With the development of Li-S batteries, more and more investigators
focused on the field of MOF-derived materials. For example, Hao and co-
workers exploit a multilayer graphene sheets stack, by calcining MOF at
500 or 900 ◦ C for 1.0 h with a heating rate of 1 ◦ C min− 1 in argon at­
mosphere [177]. When the material was used as a cathode host in Li–S
batteries, it can retain an outstanding Coulombic efficiency of 100%. Its
hierarchically porous structures can play a significant role in absorb or
fix sulfur. Subsequently, Li’ group reported the effect of sulfur fixation in
MOF-derived carbon of layered mesopore and micropore on the elec­
trochemical performance of Li-S batteries [178]. They obtained MOF-
derived carbon by annealing ZIF-8 at 1,000 ◦ C for 5 h with a heating
rate of 5 ◦ C/min in Ar. The ZIF-8 derived N-doped carbon spheres can
possess abundant micropores of 0.5 nm and mesopores of 22 nm. Thus,
the material showed a good specific capacity of 1,008.7 mAh g− 1 at 335
mA g− 1 after 50th cycle, and an excellent cycling performance. The
Nitrogen doping of the material has many advantages with the better
ability for sulfur immobilization and the remarkable interaction be­
tween carbon and sulfur species. Recently, Zhao et al. successfully
synthesized a new MOF-derived material [179]. They firstly synthesized
a sulfurized polyacrylonitrile (SPAN) film by the in situ growth of ZIF-67
on electrospun fibers composed of PAN and CNTs. Then, the as-prepared
Fig. 9. (a) Schematic of the Zn-based MOF@GO
separator. Reproduced ref. [171]. (b) SEM of
BC@UiO-66 composite aerogel film. Inset: photo­
graph of BC@UiO-66 composite aerogel film. (c) SEM
of BC@UiO-66@PDA composite aerogel film. Inset:
photograph of BC@UiO-66@PDA composite aerogel
film. (d) TEM of BC@UiO-66@PDA nanofiber.
Reproduced ref. [173]. (e) the long-term cycling per­
formance of Li-S cell with MOF-PAN/rGO-PAN sepa­
rator at 5C for 600 cycles. (f) the high loading test of
Li-S cells with MOF-PAN/rGO-PAN separator. Repro­
duced ref. [70].
Y. Jiang et al. Electrochemistry Communications 122 (2021) 106881

Table 2
Summary of MOF derivatives for Li-S batteries.
Electrode material MOF template Initial DischargeCapacities (mAh g− 1) Reversible Capacity (mAh g− 1) Refs.

UHCS Cu-MOFs – ~600 at 1C over 100 cycles [177]

1
NDC/S ZIF-8 1509.1 at 335 mA g− 936.5 at 335 mA g− 1 over 100 cycles [178]
CoS2–SPAN–CNT ZIF-67 1610 at 0.2C 880 at 1C over 400 cycles [179]
HPC/S Al-PCP 1774 at 0.1C 690 at 0.1C over 50 cycles [180]
S/FLHPC Al-MOF 1206 at 0.1C 751 at 0.5C over 200 cycles [181]
S/CHPCF Cu-MOF 1336 at 1C 547 at 2C over 500 cycles [182]
S/HKC HKUST-1 960 at 2C 547 at 2C over 500 cycles [182]
S/MoS2@HCS Ni-BTC 700 at 2C 733.6 at 0.2C over 500 cycles [183]
S@Ni2P/NC MOF-74(Ni) 1357 at 0.2C 796 at 1C over 1000 cycles [184]
S@Na2Fe[Fe(CN)6]@PEDOT PBA 717 at 5C 544 at 5C over 200 cycles [185]
S@Co-GC ZIF-67 1376 at 0.05C 382 at 1C over 200 cycles [186]
S@Co/ACN ZIF-67 – 275 at 1C over 500 cycles [186]
S@Co-N-GC ZIF-67 1670 at 0.05C 625 at 1C over 500 cycles [186]
Fe3O4@C MIL-53 760 at 1C 755 at 1C over 300 cycles [187]
c-CN Ni-based MOFs 1532.1 at 0.2C 645.9 at 2C over 400 cycles [188]

precursor was vulcanized to get CoS2–SPAN–CNT. When the
CoS2–SPAN–CNT was used as a cathode host in Li-S batteries, it dis­
played a high discharge capacity of 1,322 mAh g− 1. In addition, the
surface decoration of CoS2 can improve the electrical conductivity of the
material. Subsequently, Gao and co-workers reported a novel ZIF-67-
derived material (PZ67). Benefiting from its unique structure of sand­
wich structure, it exhibited an initial capacity of 1,158.1 mAh g− 1 and
retained at 715 mAh g− 1 after 300 cycles. Furthermore, numerous
metal-based MOFs as cathode materials, including Al-MOF [180,181],
Cu-MOF [182], Ni-MOF [183,184], Prussian blue analogues [185], etc.
(Table 2) have been well matched with carbon materials, some of them
delivered promising energy density.
In summary, MOFs are acknowledged as active cathode materials or
functional separators for Li-S battery because of their well-defined
porous structure and chemical, mechanical, and thermal stability. The
reasonable design of efficient host MOFs can improve the fixed sulfur
capacity. Even, some MOFs and MOF composites can solve the rapid
capacity degradation. Moreover, the good porosity of MOF materials can
ensure excellent sulfur loading capacity. But, the surface area and par­
ticle size as well as conductivity of MOF materials can influence the
performance of Li-S battery. The different particle sizes of MOF mate­
rials can be acquired by using special synthesis methods, and the
improved conductivity can be obtained by introducing different
conductive agents to MOF materials, such as CNTs, GO, etc. To obtain
the good specific capacity and excellent cycling ability, MOFs with
different coordination metal centers or nanostructures can be studied.
5. Application of MOF materials in Li-O2 batteries
Li-O2 battery has become a potential direction for the development
of batteries due to its extremely high theoretical energy density and
sufficient oxygen sources in electrochemical reactions. Therefore, the
literature in this field is now rarely reported. MOFs are widely used in Li-
O2 battery (Table 4) due to its high porosity and adjustable framework
components [35]. Compared with LIBs, Li-O2 battery can offer higher
weight energy (from 3 to 5 times) [189]. And Li-O2 battery possesses
theoretical energy density (5,200 Wh kg− 1) better than Li-S battery
[189]. Li-O2 battery work obviously on the same principle as the other
lithium-based batteries with the only difference being in the reaction
between lithium (contained in the anode) and oxygen (present in the air)
to form LiO2 and Li2O2 [190]. The Li-O2 batteries contain two reactions:
oxygen evolution reaction (OER) and the oxygen reduction reaction
(ORR).
In order to a better oxygen reduction mechanism for Li-O2 batteries.
This needs to prevent CO2 and water from entering the battery cathode
along with O2. Because CO2 and water will cause side reactions to occur
at the cathode, and leading to rapid degradation of the battery. Hence,
one of the effective strategies for addressing this issue is to use a
membrane, which can selectively O2 to pass, while preventing water and
CO2 from entering the battery. For instance, In 2015, Cao et al. [191]
obtained a new mixed matrix membrane (MMM) through incorporating
the polydopamine (CAU-1-NH2@PDA) and the MOF crystals of CAU-1-
NH2 into the PMMA matrix. This MMM can inherit the advantages of the
CAU-1-NH2 and the PMMA. Thus, this MMM can highly adsorb CO2 and
prevent H2O from entering the electrode. Even, it also has good O2
permeability. The functional diagram of MMM is shown in Fig. 10a. Due
to these advantages, the MMM cathode showed an excellent discharge
capacity of 1,480 mAh g− 1 at 200 mA g− 1. Compared with the pristine
cathode, the MMM cathode is much better. This method can ensure that
ORR responds better. So, Li-O2 batteries can have a better performance.
Subsequently, Hu and his colleagues synthesized a new MOF mate­
rial called Ni(4,4′ -bipy)(H3BTC) as an active cathode catalyst [192]. The
crystal structures of Ni-MOFs are shown in Fig. 10b. The Ni-MOFs can
ensure O2 shuttle everywhere and efficient contact between electrolyte
and catalyst because of its three-dimensional nanostructure, high sur­
face area and open active site. Test results showed that this cathode
catalyst exhibited a good capacity of 9,000 mAh g− 1 at 0.12 mA cm− 2.
Even, in 170 cycles, the voltage did not drop significantly. In addition,
when the Ni-MOFs was used as active cathode catalysts, Li-O2 batteries
showed a good energy density of 478 Wh kg− 1. This active cathode
catalyst can become a good example in Li-O2 batteries development. To
gain a better performance, Wu and co-workers investigated some new
MOFs (i.e. HKUST-1, MOF-5, and M− MOF− 74 (M = Mg, Mn, Co) as
active cathode materials [193]. Their crystal structures are shown in
Fig. 10c. They have the characteristics of large surface area, unique
metal locations and many kinds of structural topologies. Among these
MOFs, the Mn-MOF-74 possesses one-dimensional open channels and a
large number of open metal sites. Test results displayed that it exhibited
a primary capacity of 9,420 mAh g− 1 at 50 mA g− 1 under one atmo­
sphere of oxygen. Even at 200 mA g− 1, it also exhibited six complete
cycling performance (Fig. 10h). These open metal sites in the uniform
channel enhance the number of oxygen molecules in the pore and
effectively promote the reaction to achieve good performance because of
its open metal site. In 2018, Kim et al. [194] prepared a bimetallic
MnCo-MOF-74 via using a simple hydrothermal approach. Compared
with above single metal Mn-MOF-74, the bimetallic MnCo-MOF-74
showed a better reversible capacity. During charging and discharging,
it also exhibited an efficient cycle capacity due to its Mn-metal and Co-
metal clusters. The electron microscope images of the M− MOF− 74 (M
= Mn, Co, MnCo) are shown in Fig. 10d-g. When the MnCo-MOF-74 was
used as cathode catalysts, test results showed that it displayed an
outstanding discharge capacity of 11,150 mAh g− 1 at 200 mA g− 1. Even,
after 44 charge–discharge cycles, it still achieved a good discharge ca­
pacity of 1,000 mAh g− 1. In addition, this material can play a promoting
role in ORR and OER.
MOFs-derived materials are also used as active cathode catalysts in

16
Y. Jiang et al.
Li-O2 batteries (Table 3). MOF derivatives can show enhanced electro­
chemical performance. For instance, Liang et al. successfully synthesized
a porous MOF-derived nitrogen-doped carbon material [195]. They
obtained the material by annealing as-prepared Zn, Co-ZIF@mSiO2 at
800 ◦ C for 2 h under an inert gas atmosphere. The material retained the
structure of the MOF precursor, which can promote the formation of
catalytic sites. Thus, the material exhibited a high capacity of 5,288
mAh g− 1 and an outstanding cycle stability (no apparent decay over 500
cycles). Subsequently, Yin’ group reported a novel hierarchical meso­
porous ZnO/ZnFe2O4/C (ZZFC) nanocages by utilizing Fe(III)-MOF-5 as
a template [196]. When the MOF derivative was used cathode catalyst, it
showed a large specific capacity and a remarkable cycling performance,
benefiting from its hierarchical porosity and uniformly dispersed active
sites. In addition, Lyu and co-workers successfully prepared a 3D-printed
MOF-derived hierarchically porous material via appropriate annealing
[197]. The porous material contained a hierarchically porous network,
even it has abundant micrometer-sized pores and micropores with Co
nanoparticles. Therefore, the discharge capacity can be enhanced, and
the decomposition of insulating Li2O2 can also be promoted. MOF-
derived materials are also an emerging direction as active cathode cat­
alysts in Li-O2 batteries. Thus, the investigators also need to further
research the application of MOF-derived materials in Li-O2 batteries.
Table 3
Summary of MOF derivatives for Li-O2 batteries.
Electrode material MOF template Initial DischargeCapacities (mAh g− 1)
Co, N-CNF Zn, Co-ZIF 5288 at 100 mA g− 1
ZnO/ZnFe2O4/C Fe(III)-MOF-5 11,000 at 300 mA g− 1
3DP-NC-Co Co-MOF 1,124 at 0.05 mA cm− 2
Ru-MOF-C Ru-MOF 800 at 500 mA g− 1
Co3O4 ZIF-67 15,500 at 500 mA g− 1
17
Electrochemistry Communications 122 (2021) 106881
Fig. 10. (a) The schematic illustration of the MMM
based on CAU-1-NH2@PDA and PMMA polymer for
rebelling H2O and CO2 molecules. Reproduced ref.
[191]. (b) Crystal structures of Ni-MOFs along the c
axis, perpendicular to the c axis and along the b axis.
Reproduced ref. [192]. (c) Crystal structures of MOF-
5, HKUST-1, M− MOF− 74, and a view of the 1D
channel (yellow cylinder) in M− MOF− 74. Repro­
duced ref. [193]. (d) The SEM images of Mn-MOF-74,
(e) Co-MOF-74, and (f) MnCo-MOF-74; (g) EDS map­
ping images of MnCo-MOF-74 Reproduced ref. [194].
(h) Cycling response of the Mn-MOF-74 at 200 mA
g− 1. Reproduced ref. [193]. (For interpretation of the
references to colour in this figure legend, the reader is
referred to the web version of this article.)
In summary, MOFs are a reasonable choice as cathode active mate­
rials, because the optimized structures of MOFs retain large surface
areas, adjustable structure, and good functionality. Even these MOFs can
be designed to offer consistently diffused catalytic active sites and high
conductivity. These excellent capabilities are conducive to consolidating
the performance of Li-O2 battery. In addition, the large surface area of
MOFs can provide enough place to store and transfer O2, and the
adjustable pore size and open channel of MOFs are conducive to
adsorbing O2. In the future, the multi-functional of MOF can be further
designed as an active cathode material for Li-O2 battery.
6. Conclusions and perspectives
MOFs can become most promising potential materials in lithium-
based batteries (i.e. LIBs, Li-S batteries, and Li-O2 batteries) in terms
of their adjustable pore structure, large porosity, high specific surface
area, and diverse structure. Therefore, profound insights into knowledge
behind MOF metal-ligand center/nanocomposites are crucial for the
progress of promising materials in lithium-based batteries. Firstly, the
development of history and principle of lithium-based batteries were
reviewed. Then, the performance of MOFs can be enhanced via
designing different metal-ligand center and porous structure. The MOF
Reversible Capacity (mAh g− 1) Refs.
~440 at 100 mA g− 1
over 500 cycles [195]
5,000 at 300 mA g− 1
over 15 cycles [196]
– [197]
~800 at 500 mA g− 1
over 800 cycles [198]
1,000 at 500 mA g− 1
over 132 cycles [13]
Y. Jiang et al. Electrochemistry Communications 122 (2021) 106881

Table 4
Summary of MOFs and their composites for lithium-based batteries.
Materials Initial Coulombic Efficiency (100%) Reversible Capacity (mAh g− 1) Application Refs.

MIL-53(Fe) – – LIB–cathode [83]

MIL-101(Fe) 79 – LIB–cathode [85]
MIL-88B(Fe) 79.2 744.5 at 60 mA g− 1 over 400 cycles LIB–anode [86]
Fe-MOF/rGO(5%) 43.3 1,010.3 at 500 mA g− 1 over 200 cycles LIB–anode [77]
LiFePO4/C – – – [53]
Co2(OH)2BDC 72.8 650 at 50 mA g− 1 over 100 cycles LIB–anode [89]
Co-BDC MOF 39.7 1,090 at 200 mA g− 1 over 100 cycles LIB–anode [90]
CoBTC-EtOH 49.1 473 at 2000 mA g− 1 over 500 cycles LIB–anode [91]
S-Co-MOF 80.4 1,021 at 100 mA g− 1 over 200 cycles LIB–anode [92]
Co2(DOBDC) 56 878.5 at 100 mA g− 1 over 100 cycles LIB–anode [93]
CoCOP 68.3 573 at 1,000 mA g− 1 over 1,000 cycles LIB–anode [94]
CoCGr-5 75.4 818 at 1000 mA g− 1 over 400 cycles LIB–anode [78]
Co(L) MOF/rGO 98 206 at 500 mA g− 1 over 330 cycles LIB–anode [97]
Mn-LCP – 390 at 100 mA g− 1 over 50 cycles LIB–anode [98]
Mn-BTC MOF 40 694 at 103 mA g− 1 over 100 cycles LIB–anode [99]
Cu(2,7-AQDC) 71.4 105 at 100 mA g− 1 over 50 cycles LIB–cathode [102]
Cu3(BTC)2 MOF ~100 474 at 383 mA g− 1 over 50 cycles LIB–anode [103]
Cu-TCA 96.5 39.9 at 0.5C over 200 cycles LIB–cathode [104]
Ni-MOF 100 620 at 100 mA g− 1 over 100 cycles LIB–anode [106]
Ni-Me4bpz 43.7 120 at 50 mA g− 1 over 100 cycles LIB–anode [105]
MOF-177 30 – LIB–anode [68]
BMOF ~80 190 at 100 mA g− 1 over 200 cycles LIB–anode [110]
MIL-47 ~100 70 at C/12 over 50 cycles LIB–cathode [111]
Cd(II) MOFs 78.4 36.7 at 100 mA g− 1 over 50 cycles LIB–cathode [112]
ZIF-8 32.8 349.2 at 500 mA g− 1 over 20 cycles LIB–anode [113]
Ni3(HCOO)6/CNT-50 31 560 at 300 mA g− 1 over 400 cycles – [79]
Mn-MOF/rGOn 43.7 715 at 100 mA g− 1 over 100 cycles LIB–anode [101]
SnO2@MOF/graphene 47 450 at 1,000 mA g− 1 over 1,000 cycles LIB–anode [116]
S/ZIF-8 ~70 553 at 0.5C mA g− 1 over 300 cycles LSB–cathode [161]
S@MOF-ZIF-8 75 712.5 at 0.5C mA g− 1 over 250 cycles LSB–cathode [162]
S@MOF-525(Cu) ~85 704 at 0.5C over 200 cycles LSB–cathode [163]
S–Zn-MOF – 609 at 0.2C over 200 cycles LSB–cathode [165]
MIL-88A@S ~95 300 at 0.5C over 1,000 cycles LSB–cathode [167]
MIL-101(Cr)/S ~90 695 at 0.1C over 134 cycles LSB–cathode [170]
Ni-MOF(Ni6(BTB)4(BP)3) ~75 1,490.7 at 0.1C over 100 cycles LSB–cathode [36]
UiO-66 ~99 399.6 at 1,000 mA g− 1 over 800 cycles LSB–cathode [34]
S@Ni3(HITP)2 ~95 848.9 at 0.2C over 100 cycles LSB–cathode [168]
Zn-based MOF@GO 98.8 657 at 1,673 mA g− 1 over 1,000 cycles – [171]
B/2D MOF-Co 99.7 1,112 at 0.1C over 600 cycles – [172]
BC@UiO-66 ~95 634 at 0.5C over 100 cycles – [173]
BC@UiO-66@PDA ~90 739 at 0.5C over 100 cycles – [173]
ZIF/CNFs – 1,334 at 1C over 300 cycles – [174]
MOF-PAN/rGO-PAN – 356 at 5C over 600 cycles – [70]
MMM ~100 450 at 450 mA g− 1 over 66 cycles – [191]
Ni(4,4′ -bipy)(H3BTC) ~95 600 at 0.6 mA cm− 2 over 170 cycles LOB-cathode [192]
Mn-MOF-74 ~100 – LOB–cathode [193]
MnCo-MOF-74 ~100 1,000 at 200 mA g− 1 over 44 cycles LOB–cathode [194]

materials as promising materials can maintain their own frame structure
during the insertion of lithium ions, which retain stable cycling perfor­
mance. Furthermore, MOFs with different types of unique structural
topologies and adjustable pore size, serving as host materials or catalysts
in Li-S batteries and Li-O2 batteries were summarized. In storing lithium
ions MOFs not only fix and capture sulfur through the interaction of
weak host and guest, but also provide an efficient pathway for oxygen
diffusion as well as the reduction/evolution of reaction sites. Despite
considerable achievements have been made so far, there are still several
challenges in this field:
(i) MOFs composed of variable valence metal ions and redox active
ligands can improve Li+ ions insertion in LIBs. However, LIBs will
not have better electrochemical performance, owing to the low
conductivity and insulation of the MOFs. In addition, the elec­
trical conductivity should be considered since it greatly affects
the reaction kinetics and electron-transfer rate. Thus, these de­
ficiencies need to be solving by a suitable method (e.g.,
combining with some other materials, MOF-derived materials).
(ii) MOFs constructed with Lewis acidic OMSs and Lewis basic
organic ligands are more favorable for sulfur storage and poly­
sulfides confinement in Li-S batteries. Yet, a common drawback
of the direct utility of MOFs as a host is the low electrical con­
ductivity. Hence, the development of highly conductive MOFs/
MOF composites and MOF-derived materials can be carefully
designed.
(iii) In Li-O2 batteries, H2O and CO2 also can’t be completely blocked
or absorbed. Thus, MOFs can further combine with the carbon-
based substrates, and MOFs can also be developed into nano­
structured materials. It is also important to make suitable struc­
tural modifications in MOFs. Finally, investigators can synthesis
MOFs selective by combining different materials or using a suit­
able strategy.
(iv) Benefiting from their attractive features (e.g., versatility, adjust­
ability, and functionality), MOFs can become a very remarkable
electrode material for battery. Yet, the morphology and structure
of electrode material are very important parameters for the
insertion of Li+ in battery [199]. Even, they can significantly
influence the electrochemical performance of cell. In addition, in
an industrial production environment, many current MOF ma­
terials production processes have high cost and low productivity.
Therefore, the particle size can be reduced to the nanoscale via an
appropriate approach, or a new layered nanostructure can be
built. And this can be addressed by synthesizing MOFs with

18
Y. Jiang et al.
cheaper raw materials that are abundant in nature or easily
extractable. The use of hybrid solvents in place of expensive
organic solutions may also help in cutting down the product cost.
CRediT authorship contribution statement
Yongchao Jiang: Writing - original draft. Haitao Zhao: Writing -
original draft. Luchao Yue: Writing - original draft. Jie Liang: Re­
sources, Validation. Tingshuai Li: Resources, Validation. Qian Liu:
Resources, Validation. Yonglan Luo: Resources, Validation. Xiangzhe
Kong: Resources, Validation. Siyu Lu: Resources, Validation. Xifeng
Shi: Resources, Validation. Kun Zhou: Resources, Validation. Xuping
Sun: Writing - review & editing.
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 work was supported by the National Natural Science Foundation
of China (Nos. 22072015 and 51706114).
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