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Battery Materials
Highly Processable Covalent Organic Framework Gel Electrolyte
Enabled by Side-Chain Engineering for Lithium-Ion Batteries
Ziya Liu+, Kun Zhang+, Guoji Huang, Bingqing Xu,* You-lee Hong, Xiaowei Wu,
Yusuke Nishiyama, Satoshi Horike,* Gen Zhang,* and Susumu Kitagawa
Abstract: Although covalent organic frameworks (COFs) with
a graphene-like structure present unique chemical and physical
properties, they are essentially insoluble and infusible crystal-
line powders with poor processability, hindering their further
practical applications. How to improve the processability of
COF materials is a major challenge in this field. In this
contribution, we proposed a general side-chain engineering
strategy to construct a gel-state COF with high processability.
This method takes advantages of large and soft branched alkyl
side chains as internal plasticizers to achieve the gelation of the
COF. We systematically studied the influence of the length of
the side chain on the COF gel formation. Benefitting from their
machinability and flexibility, this novel COF gel can be easily
processed into gel-type electrolytes with specific shape and
thickness, which were further applied to assemble lithium-ion
batteries that exhibited high cycling stability.
Introduction
Polymer gels are composed of three-dimensional polymer
networks and solvent that have been widely utilized in diverse
scenes with multi-purposes. The intrinsic cross-linked spatial
network structure makes them insoluble and maintains
a specific shape.[1] Benefit from large amounts of solvophilic
groups, polymer gels can be swollen by the solvent to reach an
equilibrium volume. Through rational molecular design and
[*] Z. Liu,[+] Dr. K. Zhang,[+] Dr. G. Huang, Dr. B. Xu, Dr. X. Wu,
Prof. G. Zhang
School of Chemistry and Chemical Engineering, Nanjing University
of Science and Technology
Nanjing, Jiangsu 210094 (China)
E-mail: bingqingxu@njust.edu.cn
zhanggen@njust.edu.cn
Prof. S. Horike, Prof. S. Kitagawa
Institute for Integrated Cell-Material Sciences, Institute for Advanced
Study, Kyoto University
Yoshida, Sakyo-ku, Kyoto 606-8501 (Japan)
E-mail: horike@icems.kyoto-u.ac.jp
Dr. Y.-l. Hong
RIKEN-JEOL Collaboration Center
Tsurumi, Yokohama, Kanagawa 230-0045 (Japan)
Dr. Y. Nishiyama
JEOL RESONANCE Inc.
3-1-2 Musashino, Akishima, Tokyo 196-8558 (Japan)
[+] These authors contributed equally to this work.
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.202110695.
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www.angewandte.org
How to cite: Angew. Chem. Int. Ed. 2022, 61, e202110695
International Edition: doi.org/10.1002/anie.202110695
German Edition: doi.org/10.1002/ange.202110695
organic synthesis strategies, polymer gels could be endowed
with multiple innovative functions, which have potential
applications in the fields of drug-controlled release systems,[2]
memory element switches,[3] artificial muscles,[4] chemical
separation,[5] environmental engineering,[6] and visual optical
sensing.[7] Thanks to their intrinsic advantages such as no
solvent leakage and evaporation, polymer gel electrolytes
(PGEs) have been intensively studied for their potential
applications in various electrochemical devices.[8] Owing to
their processible and environmentally friendly, PGEs have
shown higher performance and higher safety beyond com-
mercial liquid electrolytes.[9] However, the random structures
of traditional PGEs prevent the precise design of the
structures and understanding of the relationship between
structures and properties.
Covalent organic frameworks (COFs) represent a new
class of crystalline organic polymers with highly periodic
structures constructed by covalently linking organic building
blocks.[10] Its unique self-assembly characteristics in crystal-
line engineering exhibit optimal design that facilitate precise
control over structures and functionality.[11] However, COF
materials are normally highly cross-linked crystalline powders
that are insoluble and infusible and difficult to process, which
limits further practical applications in many fields. Although
COFs can be processed into films or membranes by chem-
ical[12] or physical methods,[13] these methods suffer from
serious problems such as low yield, small layer area, low
concentration and instability.[14] How to improve the process-
ability of COFs materials is a major challenge in the COFs
field. Compared with solid-state materials, gel-state materials
have higher processability and flexibility for more broad
applications. However, the gelation of crystalline powder
materials remains a significant challenge. Since COFs are 2D
or 3D polymer with periodic networks, the gelation of COFs
would provide an access to predict their structures and
properties. Until now, a series of strategies have been
developed for the gelation of metal-organic frameworks
(MOFs),[15] a similar structures to COFs, by the use of binders,
polymer substrates, or mechanical stress[16] to achieve gel-
state MOFs.[17] And MOF-gel electrolyte has also been
reported in rechargeable lithium organic batteries to enhance
long cycling stability.[15] MOFs[18] and COFs[19] used in lithium
batteries reported in literature are normally powders, then
compressed into pellets as solid or quasi-solid electrolytes in
lithium batteries. Such traditional form lacks sufficient
flexibility and requires desired processability. Hence, it is
significant to explore other forms of COFs materials, such as
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flexible gel-state. However, the gelation of COFs remains
unexploited.[20]
In this contribution, we developed a bottom-up strategy
for the gelation of COF materials by means of a general side-
chain engineering process. This method takes advantages of
large and soft branched alkyl side chains as internal plasti-
cizers.[21] The morphology of COF-Gel could be regulated
effectively by designing monomers with different lengths of
branched alkyl side chains rationally. Further, the macro-
profile of COFs turns out from powder to powder-gel mixed,
and finally to gel state. This method accomplished COFs at
room temperature, different from the traditional solvother-
mal process. The relations between COF-gel structures and
properties were further investigated. Beneficial from me-
chanical and physiochemistry property, the application of the
COF gel in lithium-ion batteries was explored, which
exhibited higher performance than normal liquid electro-
lyte-based batteries.
Results and Discussion
We envision that the feasibility of prolonging the flexible
lipophilic long-alkyl chains linked in the building blocks may
realize the conversion from typical crystalline solid to novel
gel-state COFs, which is a prevalent tactic to prepare
a gelation system in the polymer chemistry field. Since the
crystalline nature of COF materials hampers severely their
applications in solution/gelation-processed field, bearing this
in mind, herein we develop a bottom-up COF gelation
strategy to remedy this problem.[22]
Figure 1. A bottom-up strategy for the synthesis of COF-Cx (x = 4, 8, 16).
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Initially, three hydrazide-based monomers with different
lengths of branched alkyl chains were synthesized, where the
branched chain-x is denoted as Cx (x = 4, 8, or 16), depending
on the number of carbon atoms comprised by the hydrazide-
based monomers (Figure 1). As expected, COF-C8 showed
a hybrid gel state, while COF-C16 was a novel gel state
polymer. On contrary, COF-C4 with a short branched chain
showed a typical solid phase, thus the introduction of
branched alkyl chains into COFs frameworks signally alter
the phase state of targeted COFs, and converted COFs from
solid to gel morphology.
The characteristic C=O stretching bands ( & 1692 cm@1)
and NH2 stretching vibrations (3401 and 3327 cm@1) almost
disappeared in FT-IR spectra of COF-Cx, indicative of full
consumption of the starting materials of aldehydes and
hydrazide-based monomers (Supporting Information, Figur-
es S1 and S2). Strong stretching vibration bands due to the
new generation of C=N linkage was observed at & 1647 cm@1
in the spectra of COF-Cx, confirming the formation of imine
bonds. The chemical structures were also verified by 1H and
13
C chemical shifts, 1H quantitative NMR, as well as 2D 1H-13C
and 1H-15N HETCOR spectra of activated COF-Cx (Fig-
ure 3 a; Supporting Information, Figures S3–S7, Tables S1–
S3). Besides the systematic down-field shifts in COF-C16 due
to elongated layer-layer spacing (discussed below), 1H and 13C
chemical shifts of COF-C16, COF-Gel and COF-Gel electro-
lyte are essentially identical, which supports that the preser-
vation of framework structures among COF-Cx (Figure 3 d;
Figure S8). Scanning electron microscopy (SEM) images
showed that COF-C4 owned sphere morphology, while
COF-C8 revealed layer stacked structure, and COF-C16
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Figure 2. The Characterization of COF-Cx. a) PXRD patterns of COF-C4 with the experimental profiles in black, Pawley refined in red, calculated in
green, and the difference between the experimental and refined PXRD patterns in blue. b) Top and side views of the corresponding refined 2D
crystal structures of COF-C4. c) PXRD patterns (Cu Ka) of COF-Cx. d) N2 adsorption-desorption isotherms at 77 K of COF-Cx. e) Forms and PXRD
patterns (Cu Ka) of COF-C8 with different drying time.
presented coral morphology (Figure S9). The dehydrated
COF-Cx samples exhibited high thermal stability, which
showed no weight loss up to 300 8C as disclosed by thermog-
ravimetric analysis (TGA) (Figure S10).
The crystalline nature and structures of COFs were
elucidated by PXRD analysis for all activated COFs (Fig-
ure 2 a). The peak positions of COF-C4 were completely
inconsistent with the peak positions of the amines and
aldehydes used, indicating that COF-C4 has been completely
formed (Figure S11). The experimental PXRD pattern for
COF-C4 exhibited the most intense peak at 3.488, which
corresponds to the (100) diffraction facet, along with other
peaks at 6.988, 9.188, 26.2088, which were assigned to the (200),
(120), (001) facets, respectively. Structural modelling and
Pawley refinement fitting suggested that COF-C4 possess an
eclipsed AA stacking manner (Figure 2 a, green curve),
demonstrating that it holds a single 1D channel within a 2D
framework, the unit cell parameters were obtained (P6 space
group, a = b = 29.72 c, c = 3.40 c, a = b = 9088, g = 12088) (Ta-
ble S4). The experimental PXRD pattern showed good
agreement with the simulated pattern, which was confirmed
by low residual values and acceptable profile differences
(Rwp = 4.04 % and Rp = 3.14 %) (Figure S12). Figure 2 b
shows the top and side views of the corresponding refined
2D crystal structures of COF-C4, and the interlayer spacing of
COF-C4 is 3.4 c. The two peaks attributed to (110) and (200)
peaks for COF-C8 and COF-C16 showed almost the same
Bragg positions as those of COF-C4 (Figure 2 c). Neverthe-
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less, the shape and strength gradually widened and weakened.
The peak corresponding to (100) also witnessed a shift to
higher 2q angles, which means that the growing branch chain
makes the COF smaller pore size. In typical, the hydrazones
and phenyl substituents provide the non-covalent interactions
necessary when self-assembling two-dimensional COF-42.
Nevertheless, these flexible lipophilic long-alkyl chains on the
periphery of hydrazones-based moieties would inevitably
promote interlayer repulsion, thus resulting in the decrease in
the crystallinity of COF-C8 and COF-C16. The expansion of
layer-layer stacking is also evidenced by NMR. Both 1H and
13
C chemical shifts of COF-C16 show the systematical down-
field shift of 0.5–1.5 ppm compared to COF-C4 in hydrazones
and phenyl substituents, indicating weaker interlayer inter-
actions in COF-C16 (Figure 3 b,c).
N2 adsorption-desorption at 77 K were used for measuring
the porosity of activated COF-Cx. The adsorption curves of
them exhibited the type I isotherm (Figure 2 d), a character-
istic of microporous materials. The BET surface area for
COF-C4 was determined to be 622 m2 g@1. The significant
reduction in the porosity of COF-C8 and COF-C16 may be
due to the filling of long-alkyl chains into COF pores, which
hinder the access by nitrogen.
To study the crystalline quality of COFs in different forms,
COF-C8 in different stages (just formed (0 h), vacuum drying
after 1 h and 3 h) were subjected to PXRD testes. Figure 2 e
revealed that as the drying time went on, the peak intensity at
(100) and (200) increased, we speculate that the residual
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Figure 3. Solid-state NMR analysis of COF-Cx. a) 1H-13C 2D heteronuclear correlation (HETCOR) spectrum of activated COF-C16. Peak
assignments and the molecular structure are also shown. b) Comparison of 1H chemical shifts between activated COF-C4 and COF-C16.
c) Comparison of 13C chemical shifts between activated COF-C4 and COF-C16. d) Comparison of the 1H NMR line shape of COF-C16 in an
activated, COF-Gel, and CGE state. Note the peaks in the 4–14 ppm region are magnified for clarity.

disorder solvents occupied in 1D channels of COFs signifi-
cantly affect the structural regularity, with the passing of the
drying time, residual solvents were gradually removed, thus
the integrality of COFs frameworks enhanced accordingly.
Local dynamics was probed by solid-state NMR. While
hydrazones and phenyl substituents are kept rigid for all the
activated COF samples, enhanced mobility is observed in
alkyl chains of COF-C16 based on the 1H T2 relaxation time
and 1H DQ filtering efficiencies (Figures S13 and S14). For
COF-C4 and COF-C8 sample, the 1H DQ filtering efficiency
of all peaks is & 30 %, which means that both frameworks and
side-chains are rigid. This is also evidenced by short 1H T2 due
to strong 1H-1H dipolar couplings. While the COF-C16
framework is rigid (1H DQ signal filtering efficiency of
& 20–30 %), the side-chain of COF-C16 exhibit low filtering
efficiency of 15 %, indicating enhanced mobility of the side-
chain (Figure S14). The local mobility also reduces 1H-1H
dipolar coupling, resulting in elongated 1H T2 of the side-
chain. Notably, while the framework keeps rigid in COF-Gel,
the mobility of sidechain is significantly enhanced (1H DQ
filtering efficiencies and 1H T2 in Figure S15). It is also evident
that 1H NMR line shape of sidechain is significantly narrowed
in COF-Gel as the enhanced sidechain dynamics reduce
heterogeneity and 1H-1H dipolar interaction (Figure 3 d). We
speculate interactions between framework acts as linkers,
helping the gel formation.
Given the remarkable simplicity and processability of
COF-Gel fabrication at room temperature, the possibility of
COF-C16 as a gel electrolyte was explored and assessed in
a quasi-solid lithium-ion battery system. After standing for
5 hours, COF-Gel was formed. From the top view (Figure 4 b)
and side view (Figure 4 c), it could be seen that the COF-C16
gel was formed in situ completely, and the appearance was
complete and smooth. Formed COF-C16 gel could be cut into
desired shapes according to various needs in subsequent
procedures, ready for further liquid electrolytes exchange and
battery assembly (Figure 4 d). The detailed preparation
process of the COF-Gel electrolyte was as follows (Fig-
ure 4 a). Firstly, the synthesized COF gel was washed by
a mixture of DOL/DME (1/1 in v/v) and liquid electrolytes
(1 M LiTFSI in DOL/DME (1/1 in v/v)) for three times,
respectively in sequence, to replace the solvents. Finally, the
COF gel was immersed into liquid electrolytes for two hours,
to transform into COF-Gel electrolyte (denoted as CGE
after). According to requirements for mechanical strength in
lithium-ion battery system, CGE was prepared with and
without commercial separator, respectively.
The electrochemical performance of CGE was evaluated
in a LiFePO4/Li full cell system both with and without
separator as matrix, to explore this COF gel application in
lithium-ion batteries. Firstly, LiFePO4/Li full cells tests were
performed at various current densities at 25 8C, using CGE
with separator. As for cycling performance at 0.5 C (areal
capacity density: 0.52 mAh cm@2), the LiFePO4-Li full cell was
cycled at 0.1 C for three cycles firstly and then cycled at 0.5 C
in the following cycles (Figure 5 a). It displayed a discharge
specific capacity of 156.1 mAh g@1 in the 4th cycle (the first
cycle at 0.5 C rate), and a coulombic efficiency of 92.87 %, and
151.7 mAh g@1 in the 759th cycle. While the contrast full cell
displayed a discharge capacity of 154.5 mAh g@1 in the 4th
cycle and 133.3 mAh g@1 in the 777th cycle. Long-term cycling
stability at 0.5 C was enhanced in CGE full cell than contrast
group, with a capacity retention comparison of 95.83 % vs.
85.30 % for over 759 cycles. The capacity retention compar-
ison was compared detailed in Figure S16. It could be seen
that the contrast group capacity retention decayed fast and
reduced to 85.30 % since 136 cycles, while CGE full cell
maintains 98.04 % for almost 422 cycles.
When the current density was further raised to 1 C, CGE
full cell still delivered a discharge capacity of 151.1 mAh g@1 in
4th cycle, and maintained a discharge specific capacity of
147.7 mAh g@1 after 1108 cycles, showing capacity retention of
97.36 % (Figure 5 b). It declined only 0.0031 mAh g@1
(0.0020 %) per cycle for over 1104 cycles. In comparison, the

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Figure 4. Detailed preparation process of the COF-Gel electrolyte. a) COF-Gel electrolyte preparation process and digital photos of each step.
b) Digital photo of COF-Gel top view. c) Digital photo of COF-Gel side view. d) Digital photo after COF-Gel is cut.

Figure 5. Electrochemical performance of CGE in a LiFePO4-Li full cell system.. a) Cycling performance of cells at 0.5 C. b) Cycling performance of
cells at 1 C. c) Rate performance of cells cycled at 0.1 C, 0.5 C, 1 C, 2 C, 5 C and 0.1 C. d) Cycling performance of cells at 5 C after rate tests.
e) Cycling performance of cells at 0.5 C without separator skeleton. f) Diagram of a CGE full cell structure.

capacity decayed fast in contrast group, from 148.4 mAh g@1 in (0.0082 %) per cycle. The details of capacity retention were
cycle 4 to 136.2 mAh g@1 in cycle 1000, implying capacity showed in Figure S18, the contrast group declined fast than
retention of 91.78 % for over 997 cycles, 0.0122 mAh g@1 CGE cell. Enhanced long-term cycling stability in CGE cell

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than in contrast group could be attributed to the electrolyte
locking ability in CGE, which could be contributed from the
unique 2D layer structure and branch C16 of COFs.
Then rate tests were adopted to investigate the cycling
stability at various current densities (Figure 5 c). CGE full cell
was cycled for 10, 20, 30, 40, 50, and 10 cycles at the rate of
0.1 C, 0.5 C, 1 C, 2 C, 5 C and 0.1 C. It obtained a specific
discharge capacity of 158.7, 151, 145.4, 137.5, 110.1 and
157.8 mAh g@1 at corresponding rates. Comparatively, under
the same circumstance, the control full cell demonstrated
lower discharge specific capacity, which was 144.8, 122, 113,
101.2, 72.5, and 148.8 mAh g@1 separately. Besides, full cells
after rate tests were further cycled at 5 C to measure the long
cycling stability at a high current density (Figure 5 d). The
specific discharge capacity reduced dramatically in contrast
group from 76.8 mAh g@1 in cycle 1 to 60.5 mAh g@1 in cycle
310 within only 310 cycles, showing capacity retention of
78.78 %. Meanwhile, CGE cell delivered a specific discharge
capacity of 108.9 mAh g@1 in 1st cycle, and maintain a high
specific capacity of 105 mAh g@1 after 311 cycles, signifying
a boosted capacity retention of 94.7 % for over 1300 cycles
(Figure S22).
In the synthesis process, CGE was prepared with a sepa-
rator as a skeleton, besides, the CGE without any separator
skeleton (denoted as CGE-I) was also fabricated and tested
for electrochemical performance. The CGE without separator
skeleton was tested at 0.1 C for three cycles and 0.5 C in
subsequent cycles (Figure 5 e). It delivered 157.8 mAh g@1 in
the 1st cycle at 0.1 C with a 70.14 % coulombic efficiency, and
it still showed 141.8 mAh g@1 when the current density turned
into 0.5 C (4th cycle). The full cell could be cycled stably for
41 cycles with a specific capacity of 136.5 mAh g@1. It demon-
strated that the CGE could operate as gel electrolyte without
extra skeleton support. A pouch cell assembled with CGE (no
separator skeleton) could power a light-emitting diode (LED)
lamp easily, demonstrating the accessibility and reliability of
CGE in pouch lithium-ion batteries (Figure 5 e inset).
To understand the composition of SEI formed on lithium
metal anode, X-ray photoelectron spectroscopy (XPS) was
used to further study the composition of the SEI layer
produced on the recycled Li metal and gel electrolyte
(Figure 5 f). As shown in Figure S26, the common compo-
nents included & 290.5 eV (C-F), polyether carbon
( & 286.7 eV (CH2O)), hydrocarbon ( & 284.8 eV (CH2-
CH2O) all appeared in C 1s spectra of lithium metal anodes
and gel electrolytes.[23] But the difference was that carbonyl
group ( & 288.1 eV(CO3)) appears in the carbon spectrum of
the lithium metal anode, and this same phenomenon has been
reported.[24] It can be seen from the F 1s spectra that the -CFx
peak existed both in the gel electrolyte and lithium metal
anode.[25] At the same time, LiF appeared in both gel
electrolyte and lithium metal anodes F 1s spectra of
& 685.2 eV.[26]
Conclusion
We have developed an effective molecular design and self-
assembly strategy for the construction of gel-state COFs with
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high processability for the first time, which overcomes the
processing difficulties of traditional COF powder materials.
This novel method is suitable for a variety of COFs and can
precisely regulate the conversion from typical solid COFs to
COF gels. The appropriately extended flexible long branched
alkyl chains linked in the rigid skeletons of COFs exaggerate
the interlayer packing and accelerate the occurrence of
gelation. The gel-state morphologies are fairly stable and
reduce molecular/ionic disorder in the COF gel, which
facilitates efficient ion transport kinetics and reduces the
interfacial parasitic reactions during the electrochemical
process. Benefitting from their high machinability and
flexibility, this novel COF gel can be easily processed into
gel-type electrolytes with specific shapes and thickness, which
exhibited long-life cycling, a much lower capacity decay rate
and considerably reduced parasitic reactions. The strategy
demonstrated here highlights the potential of novel high-
efficacy COF-Gel electrolytes in the field of energy storage.
Precise molecular design and self-assembly in the gelation of
COFs is envisaged, with enormous potential in crystalline
engineering. The discovery reported herein improves the
processability of COF materials and greatly broadens the
scope of COF applications.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (22171136), by “the Fundamen-
tal Research Funds for the Central Universities”
(30921011102), the Natural Science Foundation of Jiangsu
Province (BK20200472), the Startup Funding from Nanjing
University of Science and Technology (AD41913, AD41960),
Postgraduate Research & Practice Innovation Program of
Jiangsu Province (KYCX21_0332), State Key Laboratory of
New Ceramic and Fine Processing Tsinghua University (No.
KF202107), the Japan Society for the Promotion of Science
(JSPS) for a Grant-in-Aid for Scientific Research (B)
(JP18H02032), Challenging Research (Exploratory)
(JP19K22200), Scientific Research (S) (JP18H05262) from
the Ministry of Education, Culture, Sports, Science and
Technology, Japan. We are grateful to Dr. Songyan Bai and
Dr. Nobuhiko Hosono for preliminary studies on this general
concept. G.Z. acknowledges the support of the Thousand
Young Talents Plan.
Conflict of Interest
The authors declare no conflict of interest.
Keywords: covalent organic frameworks · lithium-ion batteries ·
polymer gel electrolytes · side-chain engineering
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Manuscript received: August 9, 2021
Revised manuscript received: October 24, 2021
Accepted manuscript online: October 28, 2021
Version of record online: December 2, 2021
T 2021 Wiley-VCH GmbH