batteries
Review
Recent Advances and Perspectives in Single-Ion COF-Based
Solid Electrolytes
Hong Zhao 1,2,† , Xiangkun Bo 3,† , Xiucai Wang 1,2 , Yaqi Ren 4 , Zhaohuan Wei 5, * and Walid A. Daoud 3, *
Citation: Zhao, H.; Bo, X.; Wang, X.;
Ren, Y.; Wei, Z.; Daoud, W.A. Recent
Advances and Perspectives in
Single-Ion COF-Based Solid
Electrolytes. Batteries 2023, 9, 432.
https://doi.org/10.3390/
batteries9090432
Academic Editor: Stefan Adams
Received: 11 July 2023
Revised: 10 August 2023
Accepted: 21 August 2023
Published: 23 August 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Batteries 2023, 9, 432. https://doi.org/10.3390/batteries9090432
1 School of Materials Science and Hydrogen Energy, Foshan University, Foshan 528000, China;
mezhaohong@gmail.com (H.Z.); wxc5168@163.com (X.W.)
2 Guangdong Key Laboratory for Hydrogen Energy Technologies, Foshan University, Foshan 528000, China
3 Department of Mechanical Engineering, City University of Hong Kong, Kowloon, Hong Kong 999077, China;
xiangkunbo2-c@my.cityu.edu.hk
4 School of Materials and Environmental Engineering, Chengdu Technological University,
Chengdu 611730, China; ryqi1@cdtu.edu.cn
5 School of Physics, University of Electronic Science and Technology of China, Chengdu 610054, China
* Correspondence: zhwei@uestc.edu.cn (Z.W.); wdaoud@cityu.edu.hk (W.A.D.)
† These authors contributed equally to this work.
Abstract: The rapid growth of renewable energy sources and the expanding market for electric vehi-
cles (EVs) have escalated the demand for safe lithium-ion batteries (LIBs) with excellent performance.
But the limitations of safety issues and energy density for LIBs continue to be obstacles to their
future use. Recently, single-ion covalent-organic-framework-based (COF-based) solid electrolytes
have emerged as a promising avenue to address the limitations of traditional liquid electrolytes and
enhance the performance of LIBs. COFs have a porous structure and abundant electron-donating
groups, enabling the construction of an available ionic conductive network. So, COFs are the subject
of extensive and in-depth investigation, especially in terms of the impacts their adjustable porous
structure and tunable chemistry on the research of ionic transport thermodynamics and transport
kinetics. In this perspective, we present a comprehensive and significant overview of the recent
development progress of single-ion COF-based solid electrolytes, highlighting their rare performance
and potential applications in solid lithium batteries. This review illustrates the merits of single-ion
conducting solid electrolytes and single-ion COF conductor-based solid electrolytes. Furthermore,
the properties of anionic, cationic, and hybrid single-ion COF-based conducting electrolytes are
discussed, and their electrochemical performance is also compared when applied in Li-ion batteries.
Finally, to solve challenges in COF-based Li-ion batteries, strategies are provided to obtain a high
lifespan, rate performance, and stable and safe batteries. This work is promising to offer valuable
insights for researchers and the energy storage industry.
Keywords: lithium-ion batteries (LIBs); solid electrolyte; single-ion conductor; covalent organic
framework (COF)
1. Introduction
The booming market for sustainable energy and the widespread adoption of electric
vehicles (EVs) have fueled the demand for high-performance lithium-ion batteries (LIBs) that
can keep pace with the changing needs of today’s consumers. However, the safety of LIBs is
a highly important and non-negligible issue, especially as more and more consumers turn to
these cutting-edge power sources for their energy needs [1–3]. Solid electrolytes promise to
significantly reduce the risk of thermal runaway and catastrophic failures [4–6], and they can
enable the use of high-capacity electrode materials, thus enhancing the energy density and
overall performance of batteries [7,8]. Additionally, polymer-based solid electrolytes offer
design flexibility, allowing for the development of more compact and versatile battery designs
for applications like wearable and flexible electronics [9,10]. Overall, solid electrolytes are a
https://www.mdpi.com/journal/batteries
Batteries 2023, 9, 432 2 of 19

key innovation that can transform the energy storage landscape, paving the way for more
sustainable and efficient energy solutions across various applications [5,11,12].
Currently, there are three main kinds of solid electrolytes, and each type of solid
electrolyte has its own advantages and disadvantages [13], as shown in Figure 1. Inorganic
solid electrolytes exhibit high ionic conductivity and excellent stability but suffer from
poor mechanical properties and processing challenges [14–16]. Despite the significant
advancements made in ionic conductivity, inorganic solid electrolytes still have issues such
as grain boundary resistance, instability at electrode interfaces, and inflexibility [17,18].
Polymer electrolytes provide better processability but may have lower ionic conductivity
and less stability [19–22], and they are prone to dendrite penetration [23,24]. Single-ion
conducting polymer electrolytes have easy processability, physical flexibility, close contact
with electrodes, adaptable chemistry, and high cation transportation capability. Thus, as a
substitute for inorganic solid electrolytes and polymer electrolytes, there has been a recent
surge in interest towards single-ion conducting polymer electrolytes [25,26]. Covalent
organic frameworks (COFs) have a tunable chemical structure and high porosity, and
COF-based solid electrolytes can achieve high ionic conductivity and tailored properties
for specific applications [27,28]. Their high thermal and chemical stability, combined with
low flammability and good mechanical properties, make them safer and more durable
than other solid electrolytes [28–30]. Furthermore, COF-based solid electrolytes hold the
potential for enhanced electrode–electrolyte interface compatibility, which can lead to
improved overall battery performance [27,31,32]. The majority of these COFs are based
on two-dimensional (2D) topologies, while the number of three-dimensional (3D) COFs
does not exceed 100 so far. Three-dimensional COF materials have enhanced specific
surface area, interconnected channels, well-exposed functional moieties, and highly tunable
structures; however, their high void framework and absence of π-π stacking affect the
crystallinity and chemical stability of 3D COFs. At present, single-ion conductive COFs
with relatively stable 2D structures are more practical. However, it is possible that with the
development of synthetic strategies, single-ion conductive COF materials with a stable 3D
structure will also be the best choice for solid-state electrolytes [33]. The development of
single-ion COF-based solid electrolytes is essential, as they have the potential to optimize
methods of energy storage and energy usage, thus contributing to a more efficient and
sustainable energy landscape in the future [27,34].
Some of the critical aspects and benefits of developing COF-based electrolyte materials
include the following: (i) Enhanced safety: This feature is particularly crucial for large-scale
battery systems, such as electric vehicles or grid energy storage [35,36]. (ii) High ionic
conductivity: Single-ion COF-based solid electrolytes can provide high ionic conductivity,
enabling efficient charge transfer within the battery [37]. (iii) Structural stability: COF-based
solid electrolytes exhibit strong covalent bonding, leading to a stable framework that can
withstand high voltages and temperatures [38–40]. (iv) Single-ion transport: Only allowing
the transport of one type of ion (e.g., lithium ions) reduces the likelihood of undesirable
side reactions, improving the overall energy efficiency and ensuring a stable voltage during
operation [41,42]. (v) Design flexibility: COFs offer a high degree of tunability in their
structure, porosity, and functionality, allowing researchers to design materials with specific
properties tailored for different battery chemistries and applications [43,44]. (vi) Environ-
mental benefits: COFs are not typically composed of heavy metal elements; for instance,
the elements carbon, hydrogen, oxygen, and nitrogen make up the majority of COFs, mak-
ing them more environmentally friendly than other types of solid-state materials [45,46].
Apart from COF compounds, materials such as metal–organic frameworks (MOFs) [47]
and zeolite [48] structures also exhibit similarities in their structural characteristics. These
materials possess high porosity and crystallinity, making them potential candidates for
various applications, including solid-state electrolytes. COFs are connected by covalent
bonds, their structure is more stable, there are no heavy atoms, their crystallinity is slightly
poor, and their pores are mostly lipophilic, which is suitable for lithium battery electrolytes.
MOFs have a similar structure to COFs, which are connected by ionic bonds and coordina-
 COFs are still regarded as having more potential as electrolytes for LIBs comp
MOFs.
Overall, the use of a COF as a solid electrolyte for LIBs offers several adv
over other solid electrolytes. Very recently, there some detailed reviews have
rized the importance and development of COF-based materials and their pract
Batteries 2023, 9, 432 plication, indicating the cutting-edge development of this kind 3 of of 19material
[49–51]. Furthermore, their scalability, cost-effectiveness, and safety concerns w
vealed, which require further exploration and optimization [52–54]. In our mini
tion bonds. Evenpaper,
though wethere
presented an evaluation
are applications of single-ion
for MOF-based COF-based
solid solid
electrolytes electrolytes,
[49], their elu
their advantages and challenges, and identifying study directions
stability is not good and most of the pores in their structures are hydrophilic as well as and opportun
zeolite. COFs arethe
stillfurther development
regarded and application
as having more potential asofelectrolytes
single-ion for
COF-based solid electrolyt
LIBs compared
to MOFs.

Figure 1. Comparison of different solid electrolytes.

Overall, the use of a COF as a solid electrolyte for LIBs offers several advantages
over other solid electrolytes. Very recently, there some detailed reviews have summarized
Figure 1. Comparison of different solid electrolytes.
the importance and development of COF-based materials and their practical application,
indicating the cutting-edge development of this kind of material in LIBs [49–51]. Further-
2. Single-Ion Conducting Solid Electrolyte
more, their scalability, cost-effectiveness, and safety concerns were revealed, which require
2.1.and
further exploration Single-Ion Conductor
optimization [52–54]. In our mini review paper, we presented an
Aside
evaluation of single-ion from the solid
COF-based transportation of Li
electrolytes, + ions, the their
elucidating movement of anions
advantages and is also a
componentstudy
challenges, and identifying of battery function
directions while in operation.
and opportunities The ion
for the further transference numb
development
evaluates
and application of single-iontheCOF-based
migrationsolid
ability of a certain ion is generally represented by the
electrolytes.

2. Single-Ion Conducting Solid Electrolyte

2.1. Single-Ion Conductor
Aside from the transportation of Li+ ions, the movement of anions is also a crucial
component of battery function while in operation. The ion transference number that
evaluates the migration ability of a certain ion is generally represented by the ratio of the
quantity of these ions in the system to the total quantity of ions, as shown in Formula (1) [55]:

Q+ Q
t+ = ; t− = − ; t+ + t− = 1, (1)
Q Q

where t+ and t− are the quantity of transferred cations and anions, respectively, while Q
is the total charge, Q+ is the amount of positive ionic charge, and Q− is the amount of
negative ionic charge. At present, the electrolyte salt LiPF6 is mainly used as the electrolyte
in commercial LIBs. During the operating (i.e., charging/discharging) process of the
 hardly solvated and move relatively quickly, as shown on the left in Figure 2 [56]. Some
studies show anions moving over four times faster than Li+ ions, and as a result, the
transferred Li + ions account for a low fraction (20%) of the total ion current [57]. This
phenomenon presents a problem whereby excessive anions accumulate on the surface of
the cathode, creating a concentration gradient between the cathode and the anode. The
Batteries 2023, 9, 432 accumulation of anions at the electrolyte–electrode interface results in cell polariza- 4 of 19

tion and a shortened cycle life [13].

A single-ion conducting electrolyte is a system in which anions are completely or
+ and PFor−removable
partiallyLitrapped, Li+
battery, 6 will move anions do not
to opposite exist (suchSolvated
directions. as an inorganic solid electro-
sheaths surround
lyte).
in the In single-ion
solution, conducting
moving +
with Li electrolytes,
and limitingthethemigration
migrationofspeed.
cations is relatively
However, −
PF6 much
ions
are hardly
faster, solvated
as shown onand
the move
right relatively
in Figure quickly, as shown
2. Single-ion on the left
conducting in Figuretend
electrolytes 2 [56].
to
Some studies
eliminate show anionsgradients
concentration moving over
and four
allowtimes
for faster than Li+ ions, and as a[58–60].
fast charging/discharging result,
the
Thetransferred Li+ ions
closer Li+ ions account for
transference a low fraction
number (20%)
is to 1, the of the
higher total
the ion current
migration ratio[57]. This
of Li + in

phenomenon presents a problem whereby excessive anions accumulate on

the electrolyte, resulting in higher charge transfer efficiency between the cathode and the surface of
the cathode,
anode. As a creating a concentration
result, the gradient number
Li ions transference
+ between canthe cathode
affect theand the anode.
cycling The
efficiency
accumulation
and capacity of ofanions at the [61–64].
the battery electrolyte–electrode interface results in cell polarization and
a shortened cycle life [13].

Figure 2. Comparison
Figure 2. Comparison of
of dual-
dual- and
and single-ion
single-ion conducting
conducting electrolytes.
electrolytes.
A single-ion conducting electrolyte is a system in which anions are completely or
2.2. Advantages of Single-Ion Conductors
partially trapped, or removable anions do not exist (such as an inorganic solid electrolyte).
Single-ion
In single-ion conducting
conducting solid electrolytes
electrolytes, are the ideal
the migration choiceisfor
of cations next-generation
relatively bat-
much faster,
teries, as they offer rapid charging capabilities, exceptional safety, and
as shown on the right in Figure 2. Single-ion conducting electrolytes tend to eliminate a high energy
density [65–67],
concentration This isand
gradients graphically
allow for represented in Figure 3a. Obviously,
fast charging/discharging [58–60]. Thesingle-ion con-
closer Li+ ions
ductors endow
transference the electrolytes
number with the
is to 1, the higher high ionic selectivity,
migration ratio of Lioxidation
+ potential,resulting
in the electrolyte, and re-
sistance
in higherto dendrite
charge efficiency between the cathode and anode. As a result, the Li+ ions
growth.
transfer
Single-ion
transference conducting
number electrolytes
can affect the cyclingcanefficiency
delay the development
and of lithium
capacity of the battery dendrites.
[61–64].
Chazalviel demonstrated that dendrite formation can arise in the space charge layer that
2.2. Advantages
is formed of Single-Ion
in diluted Conductors
solutions [68,69]. The study predicted that at high current densities,
dendrites would
Single-ion be generated
conducting solidwhen the concentration
electrolytes are the idealofchoice
Li+ ions on the interface bat-
for next-generation be-
tween as
teries, thethey
electrolyte
offer rapidand charging
electrodecapabilities,
decreased to zero. The safety,
exceptional initial and
time afor dendrites’
high energy
growth [65–67],
density is referred
Thistoisasgraphically
the Sand’srepresented
time, whichinisFigure
calculated by Formula
3a. Obviously, (2): conduc-
single-ion
tors endow the electrolytes with high ionic selectivity, oxidation potential, and resistance to
dendrite growth.
Single-ion conducting electrolytes can delay the development of lithium dendrites.
Chazalviel demonstrated that dendrite formation can arise in the space charge layer that
is formed in diluted solutions [68,69]. The study predicted that at high current densities,
dendrites would be generated when the concentration of Li+ ions on the interface between
the electrolyte and electrode decreased to zero. The initial time for dendrites’ growth is
referred to as the Sand’s time, which is calculated by Formula (2):
 2
eC0 µa+µ
Li+
τ = πD (2)
2Jµa 2

where D is the bipolar diffusion coefficient, e represents the charge, C0 is the initial concen-
tration of the electrolyte, j is the effective current density, and µa and µLi+ are the migration
rates of the anions and Li+ , respectively. As claimed by Chazalviel’s model, Sand’s time
τ empirically depends on the transferred numbers of electrons and lithium ions. By con-
suming effective current density (j) or speeding up the migration rate of lithium ions (µLi+ ),
Sand’s time is extended, which delays the production of lithium dendrites. Therefore,
methods such as adjusting the anode structure by enhancing the specific surface area of the
 centration of the electrolyte, j is the effective current density, and μa and μLi+ are the m
gration rates of the anions and Li+, respectively. As claimed by Chazalviel’s model, San
time τ empirically depends on the transferred numbers of electrons and lithium ions.
consuming effective current density (j) or speeding up the migration rate of lithium io
(μLi+), Sand’s time is extended, which delays the production of lithium dendrites. The
Batteries 2023, 9, 432 5 of 19
fore, methods such as adjusting the anode structure by enhancing the specific surfa
area of the two-dimensional material and using electrolytes with a high quantity
transferred lithium ions can restrain the formation of dendrites [70,71]. If Li+ ions
two-dimensional material
transference and using
number electrolytes
of the single-ion with a high quantity
conductor of transferred
is higher, lithium
the formation time of lithiu
ions can restrain
dendrites would be longer. So, the utilization of a high Li migrationofnumber
the formation of dendrites [70,71]. If Li+ ions 5 transference
+ number the in s
single-ion conductor is higher, the formation time of lithium dendrites would be longer.
gle-ion conductors +is one of the effective methods to inhibit lithium dendrites. In ad
So, the utilization of a high
tion, Figure Li migration
3b indicates that thenumber in single-ion
formation conductors
of the problematic andispotentially
one of the dangero
effective methods to inhibit lithium dendrites. In addition, Figure 3b indicates that the
soft Li dendrites, as well as their associated side reactions, is significantly inhibited
formation of the problematic and potentially dangerous soft Li dendrites, as well as their as-
single-ion-conductor-based cells thanks to the material’s exceptional selectivity conce
sociated side reactions, is significantly inhibited in single-ion-conductor-based cells thanks
ing Li-ion transport (μLi+ = 0.63). This is due to the fact that with s
to the material’s exceptional selectivity concerning Li-ion transport (µLi+ = 0.63). This is
gle-ion-conductor-based cells, the anion concentrations never reach zero on the ano
due to the fact that with single-ion-conductor-based cells, the anion concentrations never
interface due to the immobilized anion present [72]. Single-ion conducting electroly
reach zero on the anode interface due to the immobilized anion present [72]. Single-ion
can reduce battery polarization as well. As shown in Figure 3c, dual-ion conducting so
conducting electrolytes can reduce battery polarization as well. As shown in Figure 3c,
polymer electrolytes exhibit superior kinetic characteristics in conditions prior to t
dual-ion conducting solid polymer electrolytes exhibit superior kinetic characteristics in
occurrence of concentration polarization, but at a higher current, only the method of u
conditions prior to the occurrence of concentration polarization, but at a higher current,
lizing a single-ion conducting solid polymer electrolyte is possible to avoid the conce
only the method of utilizing a single-ion conducting solid polymer electrolyte is possible to
tration polarization within the battery system [73].
avoid the concentration polarization within the battery system [73].

Figure 3. The advantages

Figure of single-ion
3. The advantages of conducting electrolytes
single-ion conducting for preventing
electrolytes lithium dendrites
for preventing lithium dendrites
(a) [13], reducing concentration polarization [72] (b), and inhabiting Li dendrites (c) [73]. Reproduced
[13], reducing concentration polarization [72] (b), and inhabiting Li dendrites (c) [73]. Rep
with permission
ducedfrom the permission
with Royal Society of Chemistry,
from the Royal American
Society ofChemical Society,
Chemistry, and Wiley.
American Chemical Society, a
Wiley.
3. Single-Ion COF-Based Electrolytes
3.1. Li-Ion Transport Mechanisms in COFs
In ceramic solid electrolytes, the conduction pathways of Li+ ions move from one
crystal site to another through vacancies in the crystal lattice [11,74]. So, these pathways
are often referred to as “interstitial” or “vacancy” conduction. In polymer solid electrolytes,
the conduction pathways of Li+ ions are through the polymer chains. The lithium ions
move along the polymer chains by hopping from one site to another. These pathways are
often referred to as “ionic hopping” conduction [75]. Both of these conduction pathways
are essential for the effective functioning of solid-state lithium-ion batteries. They enable
the transport of Li+ ions, which is critical for the storage and release of electrical energy in
the battery. So far, there are two categories of COF electrolytes: (i) pure COFs mixed with Li
salts [76,77], and (ii) semi-solid electrolytes, which are hybrids including COFs and liquid
electrolytes. There are three forms of ion transport: (1) Li+ hopping on the same COF cluster
between the outmost oxygen [78], (2) Li+ hopping between COF clusters, and (3) solvated
 Batteries 2023, 9, 432 6 of 19

Li+ diffusion in bulk solvent [79]. In the pure COF-based electrolytes, no Li+ diffuses in bulk
solvent. However, in the COF-based semi-solid electrolytes, three forms of ion transport
exist simultaneously. Compared with pure COF-based solid electrolytes, the hybrid COF
electrolytes show better ionic conductivity. However, the quantity of transferred Li+ in
hybrid COF electrolytes is lower than that of pure COF-based solid electrolytes [74,80].
The Li+ traffic in 2D-COF solid electrolytes combines the performance of liquid elec-
trolytes and solid inorganic electrolytes. Specifically, the local environment of Li+ , as shown
in Figure 4b, similar to those in the liquid phase (Figure 4a), exhibits a flatter energy land-
scape compared to inorganic crystalline electrolytes (Figure 4c). However, the inflexible
COF skeleton hinders the extensive diffusion of solvents and anionic species, resulting in
preventing the development of clusters that affect ionic conductivity. A number of scientists
propose that electrostatic attractions prompt the ability to transport anions during diffu-
sion for Li+ -containing COF tunnels [81]. The complex nature of COF-based electrolytes,
with their multiple components of Li ions and anions (Figure 4d), or Li ions, anions, and
solvents (Figure 4e), present a major challenge for achieving efficient Li-ion transport and
preventing undesirable interfacial reactions. The development of single-Li-ion conductors
Batteries 2023, 9, x FOR PEER REVIEW 7 of
(Figure 4f) addresses this challenge, because highly efficient Li-ion transport networks are
crucial for the realization of safe and high-performance energy storage systems at room
temperature [82].

Figure 4. Illustration of a Li+ ions’ transport mechanisms in different solid electrolytes (a–c) [81], and
Figure 4. Illustration
the distribution of acations,
of anions, Li+ ions’
andtransport mechanisms
solvent in the in different
channels of COFs solid
(d–f) [82]. electrolytes
Reproduced with (a–c) [8
and the distribution
permission of anions,
from the Royal Societycations, and solvent
of Chemistry in the channels of COFs (d–f) [82]. Reproduc
and Wiley.
with permission from the Royal Society of Chemistry and Wiley.
3.2. Single-Ion COF-Based Solid Electrolytes
3.2.1. Anionic Single-Ion COF Conducting Electrolytes
3.2. Single-Ion COF-Based Solid Electrolytes
Recently, ionic covalent organic frameworks (ICOFs) have developed rapidly and
3.2.1.
beenAnionic Single-Ion
recognized COFcandidates
as promising Conducting Electrolytes
in the field of solid electrolytes. Anionic COFs
have + transference numbers than neutral COFs [83]. The skeleton structure
higher Liionic
Recently, covalent organic frameworks (ICOFs) have developed rapidly an
of the anionic COF contains negatively charged atoms [84] or is grafted with negatively
been recognized as promising candidates in the field of solid electrolytes. Anionic CO
charged functional groups [85]. Such COFs are often combined with lithium ions to form a
have higher Li+ transference
lithium-containing numbers than neutral COFs [83]. The skeleton structure
single-ion conductor.
the anionic COF contains negatively charged atoms [84] or is grafted with negative
charged functional groups [85]. Such COFs are often combined with lithium ions to for
a lithium-containing single-ion conductor.
In order to fix anions in the COF’s porous framework, two methods are common
used: the coordination anion opens up other cationic sites, or the anion is inserted d
Batteries 2023, 9, 432 7 of 19

In order to fix anions in the COF’s porous framework, two methods are commonly
used: the coordination anion opens up other cationic sites, or the anion is inserted directly
into the structure. The function of “cages” or “hosts” for nanopores in COFs facilitates the
transport ability of Li ions, since the mobility of larger anions is restrained. As shown in Fig-
ure 5a, in the imidazolate-containing COFs, the immobilization of anionic functional groups
results in a higher degree of control of the ion transport pathways, leading to improved
electrochemical performance and stability. By harnessing the conductivity derived exclu-
sively from Li+ transfer, single-ion conducting solid electrolytes achieve higher transference
numbers and facilitate faster charging and discharging. Ultimately, these advancements
pave the way for safer, more efficient, and longer-lasting energy storage systems [84]. Fur-
thermore, as shown in Figure 5b, lithium sulfonated COFs (TpPa-SO3 Li) as solvent-free
and single-lithium-ion conductors, represent a major breakthrough in this regard. The
exceptional performance of TpPa-SO3 Li can be attributed to its strategically crafted func-
tional ion channels, a high concentration of Li+ ions, and anion groups linked covalently.
These factors combine to produce ionic conductivity of 2.7 × 10−5 S cm−1 , coupled with Li+
ions transference number reaching 0.9 at ambient temperature [86], which is higher than
that (tLi + = 0.881) of Polymer electrolytes (PEs) [87]. As shown in Figure 5c, the hydrazone-
based COF modified with a phenol group was synthesized through an innovative approach,
which led to the achievement of two important milestones: Firstly, the attainment of ion
conductivity (10−5 S cm−1 ) even at extremely low temperatures of −40 ◦ C. This remarkable
level of conductivity was accompanied by a high quantity of transferred Li+ (0.92), further
highlighting the excellent performance of this solid electrolyte [88]. As shown in Figure 5d,
incorporating flexible chains of oligo(ethylene oxide) into the structure of the porous walls
of COFs has also been reported. The TPB-DMTP-COF was accomplished by condensation
of 1,3,5-tri(4-aminophenyl)benzene (TPB) with 2,5-dimethoxyterephthalaldehyde (DMTP)
or 2,5-bis ((2-methoxyethoxy) methoxy)terephthalaldehyde (BMTP). Upon complexation
with lithium ions, the oligo(ethylene oxide) chains form a polyelectrolyte interface within
the nanochannels and provide a solution for the transportation of lithium ions [78]. The
ion conductivity of these materials was boosted by more than 103 -fold, representing a
significant breakthrough in materials science. The enhanced conductivity was attributed to
the unique vehicle mechanism of the polyelectrolyte COFs, which facilitated the motion of
ions across the nanochannels.
It is worth mentioning that the synthesis of the lithium salt PaSO3 Li for the first
time via an acid–base reaction between a 2,5-diaminobenzenesulfonic acid monomer and
lithium hydroxide (LiOH) represents a groundbreaking achievement, as shown in Figure 5e.
Similar to this synthesis method, single Na+ -COFs and K+ -COFs were produced by utilizing
their respective salts applied as monomers. Impressively, the resulting COFs exhibited an
excellent ionic conductivity (1.6 × 10−3 S cm−1 ) at 0 ◦ C, showcasing the potential of this
approach for producing solid electrolytes with exceptional performance [89]. As we know,
the spiroborate linkage is particularly attractive as it can be readily formed through a variety
of methods, including the condensation of polyols with alkaline traborate or boric acid,
as well as through transesterification between borate and polyols in a thermodynamically
favorable manner (Figure 5f). This versatility and ease of production make COFs linked by
spiroborates an attractive option for the development of new and innovative materials for
energy storage. By leveraging the unique properties of COFs and spiroborates, it is possible
to create materials with exceptional conductivity, stability, and efficiency [90].
Batteries 2023, 9, x FOR PEER REVIEW 9 of 22
Batteries 2023, 9, 432 8 of 19

Figure 5. The molecular formula of imidazolate containing a COF (a) [84], lithium sulfonated COF
Figure 5. The molecular formula of imidazolate containing a COF (a) [84], lithium sulfonated COF
(TpPa-SO3 Li) (b) [86], hydrazone-based COF with phenol group (c) [88], COF with integrating flexible
(TpPa-SO3Li) (b) [86], hydrazone-based COF with phenol group (c) [88], COF with integrating
oligo (ethylene oxide) chains (d) [78], lithium salt (lithium 2,5-diaminobenzenesulfonate, PaSO3 Li)
flexible oligo (ethylene oxide) chains (d) [78], lithium salt (lithium 2,5-diaminobenzenesulfonate,
(e)
PaSO[89], and COF with spiroborate linkage (f) [90]. Reproduced with permission from the American
3Li) (e) [89], and COF with spiroborate linkage (f) [90]. Reproduced with permission from the

American Society,
Chemical Chemical Royal Society
Society, of Society
Royal Chemistry, and Wiley.and Wiley.
of Chemistry,
3.2.2. Cationic Single-Ion COF Conducting Electrolytes
3.2.2. Cationic Single-Ion COF Conducting Electrolytes
A cationic COF contains negatively charged atoms in the skeleton structure or is
A cationic COF contains negatively charged atoms in the skeleton structure or is
grafted with positively charged functional groups. This kind of material is first allowed to
grafted with positively charged functional groups. This kind of material is first allowed
be complex with anions, such as TFSI− or ClO4 − , and then form a more complex system
to be complex with anions, such as TFSI − or ClO4−, and then form a more complex system
with Li+ ions. Recently, a study has shown that the ionic conductivity of polyethylene glycol
with Li+ +ions.
(PEG)-Li Recently, a (as
@EB-COF-ClO study has in
shown shown
Figurethat
6a),the ionicwas
which conductivity of an
measured at polyethylene
impressive
4
glycol (PEG)-Li
− 3 +@EB-COF-ClO4 (as shown in Figure 6a), which was measured at an im-
− 1 ◦ +
1.78 × 10 S cm at 120 C, with the tLi+ of PEG-Li @EB-COF-ClO4 as high as 0.60. It is
pressive
noteworthy 1.78that
× 10the
−3 S cm−1 at 120 °C, with the tLi+ of PEG-Li+@EB-COF-ClO4 as high as 0.60.
stability performance of PEG-Li+ @EB-COF-ClO4 is excellent, without
It is noteworthy that
any decay even after 48 theh stability performance
of continuous operationof at
PEG-Li + @EB-COF-ClO4 is ◦
a high temperature of 90 excellent,
C. These
Batteries 2023, 9, 432 9 of 19

findings represent a significant advancement in energy storage, as they demonstrate the

potential for developing more stable and efficient lithium-ion batteries that can resist high
temperatures for extended periods of time [91]. Chen et al. have successfully combined a
cationic skeleton with the COF structure, which enabled us to split the Li+ ion pairs in a
framework with different properties (as shown in Figure 6b). This breakthrough discovery
led to a drastic increase in the movable Li+ concentration, thereby significantly improving
the Li+ conductivity of solvent-free electrolytes (reaching 2.09 × 10−4 S cm−1 at 70 ◦ C). This
novel approach potentially revolutionizes the energy storage field by providing a more
effective and efficient method for improving the performance of lithium-ion batteries [92].
Li et al. utilized innovative imidazolium-based monomers and Im-COF-Br in the construc-
tion of a novel cationic COF, first through a Schiff base reaction, followed by replacing the
anion of Br- with bis(trifluoromethylsulfonyl)imide ion (TFSI− ), and obtained Im-COF-
TFSI-based electrolytes (as shown in Figure 6c), which exhibited high Li+ -ion conductivities
(up to 4.64 × 10−4 at 353 K and 4.04 × 10−3 S cm−1 at 423 K), excellent thermostability, and
a stable interface between electrode and electrolyte. Most impressively, the all-solid-state
Li battery of Li/Im-COF-TFSI@Li/LiFePO4 exhibited a good initial discharge capacity and
cycling ability, reaching 123.3 mAh g−1 and maintaining 91.6% in capacity following 100
cycles, even at 80 ◦ C [93]. The introduction of a functional group (imidazolium) is also
incorporated onto the porous structure of COFs through the Schiff base reaction, which has
been sufficiently demonstrated to be a highly effective method for developing pure solid
electrolytes for the conduction of Li+ ions. This approach has resulted in the successful cre-
ation of dCOF-ImBr-Xs- and dCOF-ImTFSI-Xs-based electrolytes (as shown in Figure 6d),
which exhibit remarkable ion conductivity across a wide range of operating temperatures.
Notably, the ionic conductivity of the dCOF-ImTFSI-60-based material has been found to
reach an impressive 7.05 × 10−3 S cm−1 at 423 K [94]. In addition, Li+ conductors were
synthesized by incorporating ionic liquids (ILs) into the porous nanochannels of three kinds
of crystalline thiophene-based imine-linked COFs. These COF–IL composite electrolytes
were characterized and showed remarkable thermal stability (as high as 673 K ◦ C) and
impressive ionic conductivity (reaching 2.60 × 10−3 S cm−1 at 393 K), which are the top
values recorded for doped porous organic electrolytes. Furthermore, their specific capacity
(140.8 mAh/g at 373 K) and stable cycling ability is remarkable in COF–IL composite
electrolyte-based LiFePO4 –Li fuel cells. This COF–IL electrolytes outperform pure poly
(ethylene oxide)-based electrolytes, suggesting their vast potential for applications at high
temperatures [95].

3.2.3. Hybrid Single-Ion COF Conducting Electrolytes

Presently, practical requirements for real single-ion solid-state ion conduction remain
unfulfilled. The tightly linked Li+ ions predominantly move along the surface of the
pore walls of lithiated COFs, which implies that the large pore volume or porosity is not
ideal for effective ionic mobility because it can “dilute” the total concentration of charge
carriers [96,97]. A recent study has reported exciting developments in the field of solid-state
batteries. It has been discovered that by incorporating flexible dimethylacetamide (DMA)
chains into COF channels, the functional groups of these chains are capable of liberating Li+
ions from the stiff COF structure while decoupling the lithium salt (as shown in Figure 7
upper). The resultant altered pore environment leads to a dramatic acceleration of Li+
movement, in an ordered manner. This, in turn, leads to an excellent ionic conductivity
of 1.7 × 10−4 S cm−1 for the DMA@LiTFSI- mediated COF (DLC) electrolyte, which is
approximately 100 times higher than that of other COFs. Moreover, the DLC electrolyte
exhibits a high t+ of 0.85 at room temperature. It is worth noting that COF crystals can
be made into ultrathin and highly flexible films, which opens up possibilities for the
advancement of foldable solid-state batteries for practical demonstrations. These findings
represent a significant advancement in the development of more efficient, durable, and
practical energy storage solutions for the future [98]. Similarly, the COF-poly(vinyl ethylene
carbonate) (PVEC) composite film was designed as a flexible electrolyte (as depicted at
Batteries 2023, 9, 432 10 of 19

the bottom in Figure 7). The designed COF-PVEC electrolyte film enriched with lithium-
philictriazine
Batteries 2023, 9, x FOR PEER REVIEW and carbon–carbon double bonds within the COF structure demonstrated a
11 of 22
good ionic conductivity, reaching 1.11 × 10−4 S·cm−1 at 313 K, as well as, high mechanical
strength and dendrite growth resistance [99].

Figure 6. The molecular formula of a PEG@ cationic COF (a) [91], COF with cationic framework (b)
Figure 6. The molecular formula of a PEG@ cationic COF (a) [91], COF with cationic framework
[92], imidazolium-based COF (c) [93], and defective cationic COF (d) [94]. Reproduced with per-
(b) [92], imidazolium-based COF (c) [93], and defective cationic COF (d) [94]. Reproduced with
mission from the American Chemical Society, Royal Society of Chemistry, and Wiley.
permission from the American Chemical Society, Royal Society of Chemistry, and Wiley.
3.2.3. Performance
3.2.4. Hybrid Single-Ion
of theCOF
CellsConducting
with Single-IonElectrolytes
COF-Based Solid Electrolytes
Presently, practical requirements for
Currently, COF-based solid electrolytes are stillreal single-ion solid-state
in the early stages ofion conductionand
development re-
main unfulfilled. The tightly linked Li + ions predominantly move along the surface of the
require further research to overcome challenges related to large-scale synthesis, processing,
poreoptimization.
and walls of lithiated COFs,COF-based
Single-ion which impliessolidthat the largeapplied
electrolytes pore volume or porosity
in Li/LiFePO is not
4 batteries
ideal for effective ionic mobility because it can “dilute” the total concentration
are widely reported. Li et al. [94] constructed several 2D COFs with defect sites through of charge
carriers [96,97].
introducing A recent
imidazole study has
functional reported
groups and the exciting developments
ion-exchange strategyinof the
Br−field of sol-
and TFSI −,
id-state batteries.
reaching It hasofbeen
a conductivity 7.05 discovered
− 3
× 10 S/cm thatat by
423incorporating
K and appliedflexible
in LiFePOdimethylacetam-
4 -based Li-ion
ide (DMA)
batteries, chains
with into COFcapacity
a discharge channels,ofthe functional
441.3 mAh/ggroups of these
and 98.3% chainsover
capacity are capable of
40 cycles.
liberating Li+ ions from the stiff COF structure while decoupling the
In addition, for high-voltage Li-ion batteries, Niu et al. [100] prepared a high-voltage lithium salt (as
shown in Figure 7 upper). The resultant altered pore environment leads to a dramatic
acceleration of Li + movement, in an ordered manner. This, in turn, leads to an excel-
lent ionic conductivity of 1.7 × 10 −4 S cm−1 for the DMA@LiTFSI -mediated COF (DLC)
electrolyte, which is approximately 100 times higher than that of other COFs. More-
over, the DLC electrolyte exhibits a high t + of 0.85 at room temperature. It is worth
Batteries 2023, 9, x FOR PEER REVIEW 12 of 22

Batteries 2023, 9, 432 11 of 19

noting that COF crystals can be made into ultrathin and highly flexible films, which
opens up possibilities for the advancement of foldable solid-state batteries for prac-
stable
tical quinoline aromatic
demonstrations. Thesering COF network,
findings representwhich maintained
a significant electrochemical
advancement stability
in the de-
at a voltage of 5.6 V (compared with the voltage of Li/Li + ). After being assembled into
velopment of more efficient, durable, and practical energy storage solutions for the
an NMC811
future battery, the
[98]. Similarly, the Coulombic
COF-poly(vinylefficiency was carbonate)
ethylene greater than 99%, and
(PVEC) the capacity
composite film
did not significantly decay after 400 cycles. Wang [101] incorporated
was designed as a flexible electrolyte (as depicted at the bottom in Figure 7). The plastic crystals
de-
into three-dimensional
signed COF-PVEC electrolyte COF and applied
film the modified
enriched solid electrolyte to Li|LiCoO
with lithium-philictriazine and car- 2
batteries, achieving
bon–carbon a capacity
double bonds of 152
within themAh/g and a Coulombic
COF structure demonstratedefficiency of 97%.
a good ionicCompared
conduc-
with some inorganic cathode materials, organic cathode materials generally
tivity, reaching 1.11 × 10 S·cm at 313 K, as well as, high mechanical strength and den-
−4 −1 have better
cycle stability and can
drite growth resistance [99]. better resist volume changes and structural damage during the
insertion/extraction of lithium ions.

Hybridsingle-ion
Figure7.7.Hybrid
Figure single-ionCOF COFelectrolytes
electrolytesofof dimethylacetamide/COF
dimethylacetamide/COF(upper)
(upper)[98].
[98].InInthis
this
structure,
structure,incorporating
incorporatingflexible
flexibledimethylacetamide
dimethylacetamide(DMA) (DMA)chains
chainsinto
intoCOF
COFchannels
channelswould
wouldhelphelp
Li+
Li+ions
ionstransfer
transferfrom
fromthe
thestiff
stiffCOF
COFstructure.
structure.COF-poly(vinyl
COF-poly(vinylethylene
ethylenecarbonate
carbonate(bottom)
(bottom)[99].
[99].InIn
this hybrid film, lithium-philictriazine and carbon–carbon double bonds within the COF
this hybrid film, lithium-philictriazine and carbon–carbon double bonds within the COF structure structure
interact and increase the ionic conductivity. Reproduced with permission from Wiley and Spring-
interact and increase the ionic conductivity. Reproduced with permission from Wiley and Springer.
er.
An impressive performance of the quasi-solid-state C6 O6 |LiOOC-COF3 |Li battery
3.2.4.
was demonstratedof
Performance bythe Cells with Single-Ion
its exceptional rate behavior COF-Based Solid Electrolytes
and its excellent cyclic stability, as de-
Currently,
picted in Figure COF-based
8a. The obtainedsolid electrolytes
LiOOC-COF are still insolid
3 -based the early stageseffectively
electrolyte of development
avoided
the require
and risk of disintegration
further research of organic cathodes
to overcome in the liquid
challenges electrolyte,
related maintaining
to large-scale a more
synthesis,
stable and long-lasting
processing, and optimization. battery system. This illustrates
Single-ion COF-based thesolid
potential of solid electrolytes
electrolytes applied in for
improving
Li/LiFePO the performance
4 batteries are widely andreported.
safety of next-generation batteries. several
Li et al. [94] constructed The outstanding
2D COFs results
with
of thissites
defect studythrough
highlightintroducing
the importance of developing
imidazole new materials
functional groups and and theapproaches to span
ion-exchange
strategy of Br and TFSI , reaching a conductivity of 7.05 × 10 S/cm at 423 K and appliedof
the limitations - of conventional
- liquid electrolytes and pave the
−3 way for the advancement
inhigh-performance
LiFePO4-based Li-ion and stable all-solid-state
batteries, batteries capacity
with a discharge [82]. Theof anthraquinone
441.3 mAh/g(AQ)|LiOand 98.3% 3 S-
COF2 |Liover
capacity battery has demonstrated
40 cycles. In addition,superior rate behaviors
for high-voltage Li-ionandbatteries,
cycling stability
Niu et compared
al. [100]
to the organic
prepared AQ|LiTFSI|Li
a high-voltage stablebattery,
quinolineas evidenced
aromatic ring by their
COFrespective
network, performance
which maintained curves
in Figure 8b. The exceptional cycling stability of the AQ|LiO
electrochemical stability at a voltage of 5.6 V (compared with the voltage of Li/Li ). After
3 S-COF 2 |Li battery
+ is at-
tributed to the restraining effect that it has on the dissolution
being assembled into an NMC811 battery, the Coulombic efficiency was greater than of the AQ cathode in the
liquid electrolyte. This highlights the potential
99%, and the capacity did not significantly decay after 3400 cycles. of LiO S-COF 2 as a solid electrolyte
Wang [101] incorpo- for
enhancing the stability and performance of lithium-ion batteries,
rated plastic crystals into three-dimensional COF and applied the modified solid elec- ensuring that they can
withstand
trolyte prolonged
to Li|LiCoO usage and repeated charging cycles [102]. As shown in Figure 8c, a
2 batteries, achieving a capacity of 152 mAh/g and a Coulombic effi-
COF-based semi-solid
ciency of 97%. Compared battery was prepared,
with some inorganic which
cathode matched
materials, theorganic
high-voltage
cathodesystem
mate-of
graphite|LiNi 0.5 Mn 1.5 O 4 . This study indicated that the cycling
rials generally have better cycle stability and can better resist volume changes and performance of the anionic
COF-based
structural semi-solid
damage during electrolyte is superior to that
the insertion/extraction of of the standard
lithium ions. liquid electrolyte, with
capacity retention of 83% after 100 cycles.
Batteries 2023, 9, x FOR PEER REVIEW 14 of 22
Batteries 2023, 9, 432 12 of 19

Figure 8.8. The

Thetypical
typicalelectrochemical
electrochemical performance
performance of some
of somecellscells
withwith
single-ion conducting
single-ion sol-
conducting
id/semi
solid/semisolidsolid
electrolytes: (a) The
electrolytes: (a)obtained LiOOC-COF3-based
The obtained LiOOC-COF3-based solid electrolyte effectively
solid electrolyte avoid-
effectively
ed the risk
avoided theofrisk
disintegration of organic
of disintegration cathodes
of organic [82]. (b)
cathodes Due
[82]. (b)toDue
theto
directional ion channels,
the directional high
ion channels,
Li contents, and single-ion frameworks, LiO3S-COF2 shows exceptional Li-ion conductivity [102].
high Li contents, and single-ion frameworks, LiO3 S-COF2 shows exceptional Li-ion conductivity [102].
(c) The anionic single-ion COF conductors can strongly adsorb Mn 3+/Mn2+ and Ni2+ through the
(c) The anionic single-ion COF conductors can strongly adsorb Mn3+ /Mn2+ and Ni2+ through the
Coulomb response, reducing their destructive migration to the anode, thereby improving the cycle
Coulomb response,
performance of the reducing their(d)
battery [85]. destructive
The fixed migration
anions and to enhanced
the anode,desolvation,
thereby improving
workingthe incycle
tan-
performance of the battery [85]. (d) The fixed anions and enhanced desolvation,
dem, lead to a more reliable and consistent lithium deposition, which ultimately translates to a working in tandem,
lead to acycle
longer morelife
reliable
and and consistent
improved lithium
battery deposition, [103].
functionality which Reproduced
ultimately translates to a longer from
with permission cycle
life andthe
Wiley, improved
American battery functionality
Association for the[103]. Reproduced
Advancement with permission
of Science, from Wiley, the American
and Elsevier.
Association for the Advancement of Science, and Elsevier.
3.3. Other Organic Single-Ion Conducting Polymers
These findings suggest that the use of COF-based semi-solid electrolytes has potential
In other organic single-ion conducting polymers, anions form covalent bonds with
for improving the electric output and stability performance of lithium-ion batteries [85]. In
the polymer main chain or are fixed by interacting with anion receptors, leading to a
addition, the COF-COOH@PP separator helps to improve the CE value (Figure 8d) and
cation migration number approaching 1, thereby inhibiting the polarization of the
discharge capacity, making it a promising candidate for future battery technology. The
anion concentration. At the same time, by designing and synthesizing anions with
benefits of the fixed anions and enhanced desolvation, working in tandem, lead to more
high negative charge density or introducing strong electron-withdrawing groups to
reliable and consistent lithium deposition, which ultimately translates to a longer cycle life
increase the electron domain, the dissociation degree of lithium ions and anions is
and improved battery functionality. These findings highlight the significance of material
improved, increasing the ionic conductivity.
design and selection in the development of high-performance batteries [103].
Batteries 2023, 9, 432 13 of 19

3.3. Other Organic Single-Ion Conducting Polymers

In other organic single-ion conducting polymers, anions form covalent bonds with
the polymer main chain or are fixed by interacting with anion receptors, leading to a
cation migration number approaching 1, thereby inhibiting the polarization of the anion
concentration. At the same time, by designing and synthesizing anions with high negative
charge density or introducing strong electron-withdrawing groups to increase the electron
domain, the dissociation degree of lithium ions and anions is improved, increasing the
ionic conductivity.
A series of lithium-conducting polymer electrolytes derived from singly ionized borate
groups is shown in Figure 9a. The resulting methacrylic polymers were investigated for
their ionic conductivity, with a focus on the impact of substituent groups bonded on the
boron atom. As far as we are aware, the lithium- and borate-based polymers characterized
by their flexible and electron-withdrawing substituents have the highest recorded ionic
conductivity when applied as a lithium single-ion conducting homopolymer, noted at
1.65 × 10−4 S cm−1 (at 333 K). Moreover, they have remarkable quantities of transferred
lithium (t = 0.93) and a wide electrochemical stability window, reaching 4.2 V against
Li0 /Li+ . The polymers show potential for use in lithium battery applications [104]. Por-
carelli et al. [105] synthesized single-ion conducting polyurethanes (SIPUs) utilizing a
uniquely structured ionic liquid monomer (bis-MPTFSI), along with the adaptable chem-
istry of polyurethanes, as shown in Figure 9b. The resulting SIPU-based gel polymer
electrolytes performed extremely well in lithium metal batteries at 293 K, achieving nearly
100% efficiency over 80 cycles. These SIPUs represent a pioneering example of poly(ionic
liquid)s based on polyurethane for use in battery science. Gao et al. [106] prepared an
anionic polymer network featuring borate anions linked by branched ethylene glycol
linkers and tethered into the polymer frame, offering highly selective cation transport
and controlled cation conductivity through systematic engineering of segmental mobility
(Figure 9c). Furthermore, Figure 9d shows that a lithium-sulfonamide-based functional
surface (LiPNP) has been used as an effective electrolyte in the field of lithium metal bat-
teries. When combined with lithium bis(trifluoromethane)sulfonimide and poly(ethylene
oxide) (LiTFSI/PEO), the particles prompted a considerable effect, while the membranes
managed to maintain good ionic conductivity, marked at 6.6 × 10−4 S cm−1 . This result
suggests that all polymer-based nanoparticles can reasonably serve as novel foundational
materials for applications in solid-state lithium batteries [107,108].
As we know, some gel electrolytes have already met commercial requirements at
higher operating temperatures, but the ionic conductivity of this kind of solid-state elec-
trolyte at room temperature is still low, which limits their practical applications. Also, the
compatibility between polymer electrolytes and electrode materials—especially lithium
metal—needs urgent optimization. In comparison, single-ion COF-based solid electrolytes
have more advantages and future application potential.
Unlike single-ion COF conducting electrolytes, dual-ion COF conducting electrolytes
do not contain certain functional groups that can fix cations or anions. Li+ migrates to the
active sites of COFs and, simultaneously, anions are transferred to the opposite direction
during the charge–discharge process. To increase ionic conductivity, structural optimization
and chemical modification were proposed and applied. Zhang et al. [109] and Xu et al. [78]
arched oligo(ethylene oxide) chains in COFs applied as solid electrolytes in Li-ion batteries.
The COF provided a fast ionic conductive tunnel, and the grafted amorphous oligo(ethylene
oxide) chains became a fast ionic conductor transporting Li+ due to its disordered state.
The conductivity of this solid-state electrolyte reached 1.33 × 10−3 S/cm. Xie et al. [37]
provided a method of inserting various organics or polymer chains in one-dimensional
COF nanochannels for stability or high ionic conductivity. Xu et al. [110] provided a method
for preparing fast ion-conductor transport pathways by tailoring the pore structure of COFs
for special requirements and customization of electrolyte chains. Vazquez-Molina et al. [76]
studied the effects of mechanically extruded COFs on stability and conductivity, and they
prepared anisotropic crystals with high conductivity.
Batteries
Batteries2023,
2023,9,9,x432
FOR PEER REVIEW 1614ofof22
19

Figure
Figure 9. Lithium-based
Lithium-based conducting
conducting polymer
polymer electrolytes
electrolytes derivedderived from a singly-ionized
from a singly-ionized borate group
borate group
(a) [104]. (a) [104]. conducting
The single-ion The single-ion conducting
polyurethanes polyurethanes
(SIPUs) achieved by (SIPUs)
utilizing achieved
PEG and aby uti-
custom-
lizing PEG and a custom-designed ionic liquid monomer (bis-MPTFSI) (b) [105].
designed ionic liquid monomer (bis-MPTFSI) (b) [105]. Anionic network polymers with borate anions Anionic
network polymers
interconnected with
through boratestoichiometric
varying anions interconnected through
ratios of branched varying
ethylene stoichiometric
glycol ratios
linkers (c) [106]. The
of branched ethylene glycol linkers (c) [106]. The polymer nanoparticle electrolytes with a
polymer nanoparticle electrolytes with a functional lithium sulfonamide surface (LiPNP) synthesized
functional lithium sulfonamide surface (LiPNP) synthesized through semi -batch emulsion
through semi-batch emulsion polymerization (d) [108]. Reproduced with permission from Wiley,
polymerization (d) [108]. Reproduced with permission from Wiley, Elsevier, and the American
Elsevier, and
Chemical the American Chemical Society.
Society.
4. Conclusions and Perspectives
Unlike single-ion COF conducting electrolytes, dual-ion COF conducting electro-
Although
lytes do the basic
not contain research
certain of single-ion
functional groupsconducting
that can fixCOF-based electrolytes
cations or anions. has made
Li+ migrates
significant progress, their application is still in its infancy. Researchers must develop inno-
to the active sites of COFs and, simultaneously, anions are transferred to the opposite
vative approaches for the design, synthesis, and characterization of single-ion COF-based
direction during the charge–discharge process. To increase ionic conductivity, structural
solid electrolytes, as well as fostering interdisciplinary collaboration between materials
optimization and chemical modification were proposed and applied. Zhang et al. [109]
scientists, electrochemists, and engineers to accelerate the development and deployment
and Xu et al. [78] arched oligo(ethylene oxide) chains in COFs applied as solid electro-
of these advanced materials. Developing single-ion conducting COF-based solid-state
lytes in Li-ion batteries. The COF provided a fast ionic conductive tunnel, and the graft-
electrolytes poses various challenges that need to be addressed to pave the way for their
ed amorphous oligo(ethylene oxide) chains became a fast ionic conductor transporting
widespread application in energy storage systems. Some of these challenges include
Li+ due to its disordered state. The conductivity of this solid-state electrolyte reached
the following:
1.33 × 10−3 S/cm. Xie et al. [37] provided a method of inserting various organics or poly-
Achieving high ionic conductivity: High ionic conductivity is essential for efficient
mer chains in one-dimensional COF nanochannels for stability or high ionic conductivi-
charge transfer in electrochemical devices. Modifying the functional groups that form
ty. Xu et al. [110]
electrostatic provided
interaction a methodwith
or bonding for Li
preparing fast ion-conductor
+ can improve transport
the ion-conductive path-
sites. In
ways by tailoring the pore structure of COFs for special requirements and customization
addition, doping conductive polymers or carbon into COFs can open the electron transfer
of electrolyte
tunnels chains.
between Vazquez-Molina
different et al. [76] studied
interlayers. Furthermore, the by
inspired effects of mechanically
the study ex-
predicting that
truded COFs on stability and conductivity, and they prepared
+ anisotropic
+ crystals
short distance between anionic centers is a critical factor for Li /K hopping [111], in terms with
high conductivity.
of single-ion structure design, we should minimize the distance between anionic centers to
increase the particle conductivity.
Batteries 2023, 9, 432 15 of 19

Interface compatibility: Ensuring compatibility between solid electrolytes and elec-

trode materials is crucial for optimal device performance. This requires the development of
COF-based solid electrolytes that facilitate efficient ion transport and minimize interfacial
resistance while maintaining chemical and mechanical stability at the interface. It should
be noted that organic cathode materials also have some challenges, such as capacity fading,
short cycle life, and other issues. It is worth looking forward to the development of COF-
based solid electrolytes and organic cathode materials that will complement one another
in the future, alleviating the supply crisis of lithium-ion battery materials caused by the
shortage of cobalt [112].
Scalable and cost-effective synthesis: Developing scalable and cost-effective fabrica-
tion methods for single-ion COF-based solid electrolytes is essential for their commercial
viability. Many current synthesis strategies involve complex procedures and expensive
precursors, which can limit their large-scale production and widespread adoption.

Author Contributions: H.Z. and X.B. drafted this perspective paper, and X.W. and Y.R. revised and
enriched the content of the paper. W.A.D. and Z.W. co-organized this work and are responsible for
the overall work. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by Guangdong Provincial Key Research and Development Plan
grant number 2020B090920001.
Acknowledgments: Guangdong Provincial Key Research and Development Plan (No: 2020B090920001);
the Innovation Team of Universities of Guangdong Province (2020KCXTD011); the Engineering
Research Centre of Universities of Guangdong Province (2019GCZX002); the Guangdong Key Lab-
oratory for Hydrogen Energy Technologies (2018B030322005); the National Natural Science Foun-
dation of P. R. China (Grant No.22005052); the Innovation Team of Universities of Guangdong
Province (2022KCXTD030).
Conflicts of Interest: The authors declare no conflict of interest.

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