A Lithium Ion Highway by Surface Coordination Polymerization: In Situ Growth of Metal–Organic Framework Thin Layers on Metal Oxides for Exceptional Rate and Cycling Performance

Article abstract of DOI:10.1002/chem.201703016

A thin layer of a highly porous metal–organic framework material, ZIF-8, is fabricated uniformly on the surface of nanostructured transition metal oxides (ZnO nanoflakes and MnO₂ nanorods) to boost the transfer of lithium ions. The novel design and uniform microstructure of the MOF-coated TMOs (ZIF-8@TMOs) exhibit dramatically enhanced rate and cycling performance comparing to their pristine counterparts. The capacities of ZIF-8@ZnO (nanoflakes) and ZIF-8@MnO₂ (nanorods) are 28 % and 31 % higher that of the pristine ones at the same current density. The nanorods of ZIF-8@MnO₂ show a capacity of 1067 mAh g^?1 after 500 cycles at 1 Ag^?1 and without any fading. To further improve the conductivity and capacity, the ZIF-8-coated materials are pyrolyzed at 700 °C in an N₂ atmosphere (ZIF-8@TMO-700 N). After pyrolysis, a much higher capacity improvement is achieved: ZIF-8@ZnO-700 N and ZIF-8@MnO₂-700 N have 54 % and 69 % capacity increases compared with the pristine TMOs, and at 1 Ag^?1, the capacity of ZIF-8@MnO₂-700 N is 1060 mAh g^?1 after cycling for 300 cycles.

Full text of DOI:10.1002/chem.201703016

A Journal of
Accepted Article
Title: Lithium Ion Highway by Surface Coordination Polymerization: In
Situ Growth of Metal-Organic Framework Thin Layers on Metal
Oxides for Exceptional Rate and Cycling Performances
Authors: Yuzhen Han, Danni Yu, Junwen Zhou, Peiyu Xu, Pengfei Qi,
Qianyou Wang, Siwu Li, Xiaotao Fu, Xing Gao, Chenghao
Jiang, Xiao Feng, and Bo Wang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
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to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201703016
Link to VoR: http://dx.doi.org/10.1002/chem.201703016
Supported by

Chemistry - A European Journal
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COMMUNICATION
Lithium Ion Highway by Surface Coordination Polymerization: In
Situ Growth of Metal-Organic Framework Thin Layers on Metal
Oxides for Exceptional Rate and Cycling Performances
Yuzhen Han, Danni Yu, Junwen Zhou*, Peiyu Xu, Pengfei Qi, Qianyou Wang, Siwu Li, Xiaotao Fu,
Xing Gao, Chenghao Jiang, Xiao Feng and Bo Wang*[a]
Abstract: A thin layer of a highly porous metal-organic framework
promising candidates owing to their high theoretical capacity,
low cost and natural abundance[15]
However, based on
material, ZIF-8, is fabricated uniformly on the surface of
.
nanostructured TMOs (ZnO nanoflakes and MnO
2
nanorods) to
conversion-type electrochemical reactions, these materials
having poor inherent conductivity usually undergo phase
boost the transfer of lithium ions. The novel design and uniform
microstructure of the MOF-coated TMOs (ZIF-8@TMOs) exhibit
dramatically enhanced rate and cycling performance comparing to
their pristine counterparts. The capacities of ZIF-8@ZnO
separations
associated
with
volume
changes
upon
lithiation/delithiation processes, which lead to pulverization of the
electrode and dramatic capacity fading[ . In order to address
the above issues, many strategies have been proposed,
including constructing unique TMO nanostructures, coating
16]
2
(nanoflakes) and ZIF-8@MnO (nanorods) are 28% and 31% higher
that of the pristine ones at the same current density. The nanorods
‒
1
[17]
of ZIF-8@MnO
2
show a capacity of 1067 mAh g after 500 cycles at
A g and without any fading. To further improve the conductivity
and capacity, the ZIF-8-coated materials are pyrolyzed at 700 °C in
atmosphere (ZIF-8@TMO-700N). After pyrolysis, a much higher
capacity improvment is achieved, ZIF-8@ZnO-700N and ZIF-
@MnO -700N have 54% and 69% capacity increases compared
with the pristine TMOs, and at 1 A g , the capacity of ZIF-8@MnO
TMOs with carbon or other materials, etc. . The efficacy of
‒1
1
using MOFs and their derivatives to improve the performance of
these conversion-type anodes have been demonstrated by our
group and others[18]
.
In this work, we report an in situ method of growing a thin
layer of MOF on the surface of nanostructured TMOs (ZnO
2
nanoflakes and MnO nanorods). ZIF-8 is polymerized uniformly
N
2
8
2
‒1
2
-
‒1
7
00N is 1060 mAh g after cycling for 300 cycles.
on the surface of TMOs (Figure 1) that can boost the transfer of
Li+ and preserve the cycling stability. The novel design and
uniform microstructure of the MOF-coated oxides show much
improved rate and cycling performance over pure TMOs as
anode materials. With 20 wt% ZIF-8 coated, the ZIF-8@ZnO
anode shows a discharge capacity of 247 mAh g‒1 at a high
[
1]
Metal-organic frameworks (MOFs) , as an emerging class of
crystalline multi-functional materials with well-defined porous
structures, have attracted intensive research interest for various
[
2]
applications such as gas separation , catalysis, sensors, drug
delivery, and gas chromatography, where MOFs exhibit
‒1
current density of 1 A g , 28% higher than pristine ZnO (193
‒1
‒1
mAh g ). At an even higher current density of 2 A g , the
[
3]
impressive molecular-sized selecting ability because of their
‒
1
2
capacity of ZIF-8@MnO (438 mAh g ) is 31% higher than that
[
4]
rich porosity and versatile functionalities . Recently, inspired by
their highly diverse intrinsic configurations, MOFs are found to
be promising precursors to construct nano-architectured
‒
1
of MnO
conductivity and capacity, the ZIF-8-coated materials are
pyrolyzed at 700 °C in N atmosphere (denoted as ZIF-8@TMO-
00N). The specific capacities of ZIF-8@ZnO-700N and ZIF-
2
(335 mAh g ). In order to further improve the
2
electrode[ and electrolyte materials for lithium ion batteries
5]
[6]
7
8
5
(
LIBs), showing interesting properties in ionic conduction and
‒
1
2
@MnO -700N could be further improved to 298 mAh g and
[
7]
attractive electrochemical performance .
‒1
‒1
‒1
67 mAh g at 1 A g and 2 A g . The modified TMOs can be
In the current era of LIBs, there is an ever-growing demand for
cycled over 500 cycles without decay.
[
8]
increasing the energy and power densities . High energy/power
electrode materials[9] with enhanced rate and cycling
[
10]
performances are highly desired . In pursuit of next generation
[
11]
anode materials, transition metal oxides
(TMOs), such as
ZnO[ , MnO
12]
[13]
, Fe O and Co O
[14], are widely considered as
2
2 3 3 4
[
a]
Y. Han, D. Yu, J. Zhou*, P. Xu, P. Qi, Q. Wang, S. Li, X. Fu, X. Gao,
C. Jiang, X. Feng, B. Wang
Key Laboratory of Cluster Science, Ministry of Education of China,
School of Chemistry, Beijing Institute of Technology, 5 South
Zhongguancun Street, Beijing, 100081 (P.R. China)
E-mail: bowang@bit.edu.cn; frostfire@sina.com. Homepage:
http://bowang.bit.edu.cn
Y. Han and D. Yu contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document
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COMMUNICATION
Figure 1. Schematic of the preparation process of ZIF-8 polymerized on the
surface of transition metal oxides. The transfer route of Li+ through the MOFs
are marked as red arrows.
nanoparticles of 10~50 nm homogeneously distribute on the
surface of ZnO (Figure 3e and 3f). TEM images of ZIF-8@ZnO
also reveal the uniform coverage of ZIF-8 crystallites (Figure S2).
2
The as-synthesized MnO are composed of clusters of nanorods,
ZnO nanoflakes and MnO
through hydrothermal method developed by Yan[19] and Suib[20]
detailed methods are provided in the experimental section).
ZIF-8 was grown on the surface of TMOs using a solution
method. First, 2-methylimidazole was added to the methanol
2
nanorods were synthesized
which are ~400 nm in diameter and ~2 μm in length (Figure 3c
and Figure 3d); ZIF-8 nanoparticles (10-50 nm) grow densely on
(
the surface of MnO
ZIF-8@MnO reveals the uniform distribution of Zn and N among
Mn and O (Figure 4): MnO is completely covered by ZIF-8
2
(Figure 3g and 3h). Elemental mapping of
2
2
suspension of TMO and stirred for 2 h; Zn(NO
added, followed by another 12-h stirring. The obtained
composites were named as ZIF-8@ZnO and ZIF-8@MnO
According to the powder XRD patterns, the initial nanostructured
TMOs can be identified as ZnO (JCPDS no. 70-2551) (Figure
3
)
2
·6H
2
O was then
crystallites. PXRD, nitrogen adsorption experiments, SEM
together with TEM verify the success of the surface
polymerization of ZIF-8 on the nanostructured TMOs by adding
the ligand and metal salt in sequence: no matter the initial TMOs
share the same metal with ZIF-8 or not.
2
.
2
a) and MnO
2
(JCPDS no. 72-1982) (Figure 2b) without any
The well-defined structure of ZIF-8 on TMOs was also
evidenced by Fourier transform infrared spectrum (FTIR) (Figure
S3). Samples of TMOs stirred with 2-methylimidazole for 3 h
(after thoroughly washed with methanol) clearly show the signals
of C=C and C-H bonds, indicating the reactions between TMOs
and 2-methylimidazole. Afterwards, with the addition of
Zn(NO ) ·6H O, ZIF-8 can priority polymerize on the surface of
3 2 2
TMOs. Thermo-gravimetric analysis (TGA) and inductive
coupled plasma (ICP) emission spectrometry were used to
impurity. After ZIF-8 was polymerized on the surface of TMOs,
the diffraction of ZIF-8 can be clearly observed (Figure 2a and
2b). Nitrogen adsorption and desorption measurements were
carried out to estimate the surface areas and pore size
distributions of the nanostructured TMOs (Figure S1a and S1b)
and ZIF-8@TMOs (Figure 2c and 2d). The BET surface areas of
ZnO nanoflakes and MnO
respectively, with pore size distributing mainly within the
nanorods are 37 and 200 m2 g‒1,
2
mesopore range (5-50 nm). After surface polymerization of ZIF-8, determine the contents of ZIF-8 in ZIF-8@ZnO and ZIF-
the BET surface areas of ZIF-8@ZnO and ZIF-8@MnO rise to 8@MnO , respectively. The mass loss of ZIF-8@ZnO before
32 and 304 m2 g‒1; a sharp peak centered at ~1 nm can be
2
2
2
500 °C observed in TGA (15%, Figure S4a) can be nicely
attributed to the decomposition of ZIF-8 and the combustion of
its organic moieties in air, which is translated into a ZIF-8
figured out in the pore size distributions, coinciding with the size
of ZIF-8's micropores.
content of 20%. In addition, ZIF-8@MnO
over a broader temperature range: MnO
2
keeps losing weight
decomposes and
2
starts to release oxygen over 530 °C. Therefore it is difficult to
differentiate the contribution of weight loss by ZIF-8 in TGA;
2
accordingly, the ZIF-8 content in ZIF-8@MnO was determined
by ICP (10.5%).
To further enhance the electric conductivity and overall
capacity of the composites, ZIF-8@TMOs were pyrolyzed at
2
700 °C in N atmosphere to yield ZIF-8@TMO-700N composites.
In the powder XRD patterns of the pyrolyzed samples (Figure
S5a and S5b), only oxide phases remain. It is noted that the
detected oxide in ZIF-8@MnO
363) rather than MnO . This is ascribed to the decomposition of
MnO under high temperatures, which is consistent with the TGA
2
-700N is MnO (JCPDS no. 77-
2
2
2
result (Figure S4b). SEM observations on the ZIF-8@TMO-700N
samples (Figure 3i, 3j, 3k and 3l) reveal that the original nano-
architectures (nanoflakes/nanorods) are well-maintained,
surfaces becoming smoother. A clear boundary between ZnO
and the pyrolyzed ZIF-8 can be observed under TEM (Figure
S6): with crystalline ZnO on one side, and an amorphous phase
on the other side[21]. X-ray photoelectron spectroscopy (XPS)
was used to investigate the surface chemical components of the
pyrolyzed materials. The Zn 2p spectrum of ZIF-8@ZnO-700N
Figure 2. Powder XRD patterns of (a) ZnO, ZIF-8@ZnO and (b) MnO
@MnO . Nitrogen adsorption isotherms at 77 K of (c) ZIF-8@ZnO and (d)
ZIF-8@MnO The insert in (c) and (d) are the pore size distributions
2
; ZIF-
8
2
2
.
2
calculated by NLDFT. ZIF-8@ZnO and ZIF-8@MnO are ZIF-8-coated metal
oxides.
(
1
Figure S7a) shows two peaks at 1021.4 eV (Zn 2p3/2) and
044.4 eV (Zn 2p1/2), characteristic for Zn . The C 1s spectrum
.
2
+
The morphology of TMOs and ZIF-8@TMOs were
investigated in detail by scanning electron microscopy (SEM)
and transmission electron microscopy (TEM). As shown in the
SEM images (Figure 3), smooth ZnO nanoflakes construct a
flower-like structure with an average size of ~5 μm (Figure 3a
and Figure 3b). After the growth of ZIF-8, tiny MOF
(Figure S7b) suggests the existence of C-C, C=C, C=O and C-N
components originated from the carbonization of ZIF-8. In the
XPS spectrum of ZIF-8@MnO -700N (Figure S7c and S7d),
2
both characteristics of Mn2+ and Zn2+ can be observed: 641.5 eV
(Mn 2p3/2), 653.4 eV (Mn 2p1/2), 1021.4 eV (Zn 2p3/2) and 1044.4
eV (Zn 2p1/2). It is worth noting that the carbon proportions in
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ZIF-8@ZnO-700N and ZIF-8@MnO
2
-700N were measured to be
protection of the carbon on the surface of metal oxides, the
electrochemical performance of the ZIF-8@TMO-700N is
excellent. The porosity of the ZIF-8@TMO-700N composites
were characterized by nitrogen adsorption experiments and the
results can be found in Figure S8a and S8b.
50 % and 40% by XPS with a surveying depth of about 10 nm,
respectively. The rich carbon coverage on the surface is
assumed to provide abundant electron pathways for the
nanocomposites, enhancing the electric conductivity. Due to the
2 2 2
Figure 3. SEM images of (a-b) ZnO, (c-d) MnO , (e-f) ZIF-8@ZnO, (g-h) ZIF-8@MnO , (i-j) ZIF-8@ZnO-700N, (k-l) ZIF-8@MnO -700N.
high current densities. ZnO nanoflakes, for example, only show
a capacity of 193 mAh g−1 at 1 A g ; with ZIF-8 modification, the
-1
−
1
capacity of ZIF-8@ZnO is 247 mAh g , increased by 28%; the
pyrolyzed material ZIF-8@ZnO-700N shows an even higher
−
1
capacity of 298 mAh g , a 54% increase compared with the
original one (Figure 5a). More significantly, a ZIF-8-thin-layer
modification helps MnO
2
nanorods with a capacity of 438 mAh
g−1 at 2 A g , increased by 31% from 335 mAh g of the original
-1
−1
material; pyrolyzing the ZIF-8-modified MnO
capacity to 567 mAh g , 69% higher than the pristine MnO
2
further boosts the
−
1
2
nanorods (Figure 5b). Another advantage brought by the surface
modification is the superior cycling stability. Cycling
performances of ZIF-8@ZnO and ZIF-8@ZnO-700N at 0.2 A g−1
are shown in Figure S19a. ZIF-8@ZnO and ZIF-8@ZnO-700N
have a high capacity retention compared with pristine ZnO.
Cycling performances of ZIF-8@MnO
2
and ZIF-8@MnO
2
-700N
Figure 4. TEM images of ZIF-8@MnO
2
in (a) bright and (b) dark field. (c)
at 1 A g‒1 are shown in Figure 5c and 5d. ZIF-8@MnO
shows a
2
Elemental mapping of ZIF-8@MnO for Mn, Zn, N and O by EDS.
2
reversible capacity of 929~982 mAh g‒1 at 0.1 A g . After 60
‒1
cycles at 0.1 A g−1 without any obvious fading, the current
‒
1
density was changed to 1 A g . A gradual increase in capacity
The advantage of our surface modification is first evident in
the increased capacities of the TMO composite anodes (Figure
−
1
can be found upon further cycling at 1 A g , and the capacity
reaches 1067 mA h g−1 after 500 cycles. The gradually
increased capacity during long cycling is
5
and Figure S9); the improvement is especially significant at
a
common
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COMMUNICATION
phenomenon for TMO electrode materials. The possible reasons
could be increase of electrochemically active sites or release of
initially trapped lithium ions[14, 22]. Stable cycling is also
reduced valence of Mn, as suggested by PXRD analysis (Figure
S5b).
To verify the storage ability of electrolyte, we immersed ZIF-8
or ZnO into the electrolyte for 5 min and then removed the
electrolyte on the surface by filter paper. Liquid absorption of
ZIF-8 is 1.66 g/g, which is twice higher than pristine ZnO (0.80
g/g). The large amount liquid electrolyte absorption is
meaningful for the performance of the materials. In order to gain
insight into the effects of surface modification on the
demonstrated by the pyrolyzed sample ZIF-8@MnO
2
-700N, with
a high capacity of 1060 mA h g−1 after 300 cycles at 1 A g . To
−1
pristine MnO2, the capacity is only 700 mAh g−1 after cycling for
0 cycles at 0.2 A g−1 (Figure S19b).
6
electrochemical
properties,
electrochemical
impedance
spectroscopy (EIS) was used to study the materials. As shown
in Figure S12a and S12b, the Nyquist plots of each material,
regardless of being modified or not, consist of a semicircle in the
high-frequency region with a straight line in the low-frequency
region. The resistance of the semicircle can be attributed to the
charge transfer process (denoted as Rct), and the inclined line
can be attributed to the diffusion of lithium ions in the bulk of the
electrode material (Warburg region). Fitting the Nyquist plots
with the equivalent circuit in Figure S14 yields the Rct values
(
inserts of Figure S12a and S12b), which take the order: TMO >
ZIF-8@TMO > ZIF-8@TMO-700N. This indicates that a thin
layer of ZIF-8 or its pyrolyzed derivative facilitates the charge
transfer rates of TMOs. As reported by the other authors, MOFs
had a high ionic conductivity (3.1 × 10‒4 S cm , 27 °C) when
they were used to transfer the lithium ions[6a]. Due to the high
‒1
+
ionic conductivity of MOFs, it could boost the transfer of Li . ZIF-
has a high ionic conductivity of 3.16× 10‒4 S cm . Besides, the
‒1
8
apparent lithium ion diffusion coefficient (D), calculated from the
data in the Warburg region[23] (details see supplementary
information), doubles for the surface-modified TMOs in
comparison with the original ones (Figure S12c and S12d). The
drop in Rct and the rise in D both contribute to the enhanced
electrochemical performance seen in the battery tests (Figure 5).
To get more reasons of the higher capacities, we tested the
specific capacity of pure ZIF-8 and ZIF-8-700N (ZIF-8 is
carbonized at 700 °C). ZIF-8 has the electrochemical activity and
Figure 5. Rate capabilities of (a) ZnO, ZIF-8@ZnO and ZIF-8@ZnO-700N (0.1,
‒1
0
0
7
.2, 0.5, 1 A g ), (b) MnO
2
, ZIF-8@MnO
2
and ZIF-8@MnO
and ZIF-8@MnO
00N at 1 A g . A modified TMO (ZIF-8@TMO or ZIF-8@TMO-700N) is
2
-700N (0.1, 0.2,
‒1
.5, 1, 2 A g ); (c-d) Cycling performance of ZIF-8@MnO
2
2
-
‒1
regarded as the active material as a whole, so the current density and specific
capacity are both based on the total mass of the composite.
‒
1
the capacity of it is 90 mAh g . ZIF-8-700N has a high capacity
‒
1
of 700 mAh g . (Figure S15) The capacities of ZIF-8 and ZIF-8-
00N could contribute the whole capacities of the ZIF-8@TMO
7
and ZIF-8@TMO-700N. And we also tested the materials by
SEM after cycling for 50 cycles. The morphology of ZIF-
Galvanostatic charge-discharge voltage profiles of ZnO, ZIF-
@ZnO and ZIF-8@ZnO-700N (Figure S10a, S10c and S10e)
8
8
@TMOs and ZIF-8@TMOs-700N kept better than the pristine
are similar in both shape and voltage range, revealing typical
conversion reactions of ZnO anode; the discharge/charge
voltages are in good agreement with the cathodic/anodic peaks
observed in cyclic voltammetry (CV) measurements (Figure
S11a, S11c and S11e). These observations, in combination with
the PXRD results in Figure 2a, suggest that the surface
modification of ZnO nanoflakes by ZIF-8 with/without pyrolysis
does not change the electrochemical behaviour of the ZnO body.
TMOs (Figure S16 and S17). This is one of the evidence of the
good capacity result. And the PXRD (Figure S18) data of the
electrodes after cycling for 50 cycles which indicating good
maintenance of the ZIF-8 crystal structures throughout charging
and discharging cycles. Getting more lithium adsorption sites
and higher lithium ion diffusion coefficient are the two main
approaches to achieve a high specific capacity. The porosity of
ZIF-8 could create more lithium adsorption sites, promote a
homogeneous lithiation process, and restrict of the volume
expansion of anode materials[ . On the other hand, lithium ion
diffusion coefficient has been promoted after the polymerization
of ZIF-8 on the surface of metal oxides. The fast diffusion of Li+
into the materials is one of the reasons to get an improvement of
the specific capacity.
A
similar conclusion can be made with MnO
with/without ZIF-8 modification (Figure S10 and Figure S11). It is
noted that with the growth of ZIF-8 on the surface of MnO
nanorods, the voltage hysteresis between charge and discharge
1.2 V) is narrowed down to 0.8 V (ZIF-8@MnO ), indicative of a
2
nanorods
24]
2
(
2
promotion in electrochemical kinetics. A slight shift of the
discharge/charge voltages, as well as the cathodic/anodic peaks
in CV, higher potentials are observed for the pyrolyzed ZIF-
In order to compare our materials with other similar
nanostructured metal oxides, we collected the electrochemical
2 2
8@MnO sample (ZIF-8@MnO -700N), which may reflect the
x
data of ZnO and MnO recently reported and listed them in
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Chemistry - A European Journal
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COMMUNICATION
Figure S13 and Table S1. Compared with other materials, it is
obvious that our materials behave better at various current
densities. The results are more superior especially at the high
current densities.
In summary, we have successfully developed an in situ growth
method in methanol solution of a thin layer of MOF material, ZIF-
3 2 2
in sequence and stirred slowly for 2 h. After that, Zn(NO ) ·6H O (0.05 g)
was added and the sealed mixture was continue stirred for 12 h. The
obtained samples were washed repeatedly with methanol and then dried
in a vacuum oven at 60 °C. The pure ZIF-8 was synthesized using the
method without adding metal oxides.
Thermal annealing method: The as-synthesized ZIF-8@ZnO and ZIF-
8
, uniformly on the surface of two nanostructured TMOs, ZnO
nanoflakes and MnO nanorods, no matter the initial TMO
shares the same metal with ZIF-8 or not. The surface
modification using ZIF-8 significantly enhances the
8
@MnO
2
were heat-treated at 700 °C in a flowing nitrogen atmosphere
2
with a heating ramp of 1 °C min for 1 h.
−1
electrochemical performance of TMO anodes, especially at high
current densities: the capacities of ZIF-8@ZnO (nanoflakes) and
Acknowledgements
2
ZIF-8@MnO (nanorods) are 28% and 31% higher that of the
pristine ones. In order to further improve the conductivity and
capacity, the ZIF-8-coated materials are pyrolyzed at 700 °C in
This work was financially supported by the 973 Program
2
013CB834704; Provincial Key Project of China (Grant
No.7131253); the National Natural Science Foundation of China
Grant No. 21471018, 21404010, 21201018, 21490570); 1000
N
2
atmosphere (ZIF-8@TMO-700N). A much higher capacity
improvment is achieved after pyrolysis, ZIF-8@ZnO-700N and
ZIF-8@MnO -700N have 54% and 69% capacity increases
(
Plan (Youth)
2
compared with the bulk ones at the same current densities.
Long-term cycling stability has been demonstrated by both ZIF-
Keywords: metal organic framework • surface coordination
polymerization • metal oxide • lithium ion battery • anode
material
8
8
@MnO
@MnO
2
and ZIF-8@MnO
show a capacity of 1067 mAh g at 1 A g and
2
-700N: the nanorods of ZIF-
‒
1
‒1
2
‒
1
without any fading after 500 cycles; after pyrolysis, at 1 A g ,
the capacity of ZIF-8@MnO
‒
1
-700N is 1060 mAh g after cycling
[1]
a) B. L. Chen, S. C. Xiang, G. D. Qian, Acc. Chem. Res.
010, 43, 1115; b) K. Sumida, N. Moitra, J. Reboul, S.
2
2
for 300 cycles. Lithium ion diffusion in the surface-modified
materials is found to be facilitated, accompanied with a reduced
charge transfer resistence. By virtue of the general and facile
synthetic strategy and outstanding electrochemical performance,
we envision that TMOs with MOFs or their pyrolyzed derivatives
modified on the surface could be promising materials for high-
performance LIB anodes or electrodes of other energy storage
devices.
Fukumoto, K. Nakanishi, K. Kanamori, S. Furukawa, S.
Kitagawa, Chem. Sci. 2015, 6, 5938; c) B. Wang, A. P.
Cote, H. Furukawa, M. O'Keeffe, O. M. Yaghi, Nature
2008, 453, 207; d) M. W. A. MacLean, T. Kitao, T. Suga,
M. Mizuno, S. Seki, T. Uemura, S. Kitagawa, Angew.
Chem. Int. Ed. 2016, 55, 708.
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60 °C for 12 h.
Synthesis of MnO
into 15 mL deionized water. After that, 2.03 g of MnSO
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solution slowly and regularly using a syringe. The mixture was stirred for
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Synthesis of ZIF-8@ZnO and ZIF-8@MnO
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ZnO/MnO , 15 mL of methanol, 0.15 g of 2-methylimidazole were added
2
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Chemistry - A European Journal
10.1002/chem.201703016
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
Surface coordination polymerization:
A thin layer of a highly porous metal-
organic framework material, ZIF-8, is
fabricated uniformly on the surface of
nanostructured TMOs (ZnO
Yuzhen Han, Danni Yu, Junwen Zhou*,
Peiyu Xu, Pengfei Qi, Qianyou Wang,
Siwu Li, Xiaotao Fu, Xing Gao,
Chenghao Jiang, Xiao Feng and Bo
Wang*
nanoflakes and MnO
2
nanorods) to
boost the transfer of lithium ions.
Page No. – Page No.
Lithium Ion Highway by Surface
Coordination Polymerization: In Situ
Growth of Metal-Organic Framework
Thin Layers on Metal Oxides for
Exceptional Rate and Cycling
Performances
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