Mesoporous MnO/C-N Nanostructures Derived from a Metal-Organic Framework as High-Performance Anode for Lithium-Ion Battery

Article abstract of DOI:10.1021/acs.inorgchem.7b01486

By application of newly designed ligand 5-(3-(pyridin-3-yl)benzamido)isophthalic acid (H₂PBI) to react with Mn(NO₃)₂ under solvothermal conditions, a 2-fold interpenetrated Mn-based metal-organic framework (Mn-PBI) with rutile-type topology has been obtained. When treated as a precursor by pyrolysis of Mn-PBI at 500 °C, mesoporous MnO/C-N nanostructures were prepared and treated as an lithium-ion battery anode. The MnO/C-N manifests good capacity of approximately 1085 mAh g^-1 after 100 cycles together with superior cyclic stability and remarkable rate capacity, which is supposed to benefit from a large accessible specific area and unique nanostructures. The remarkable performances suggest promising application as an advanced anode material.

Full text of DOI:10.1021/acs.inorgchem.7b01486

Article
pubs.acs.org/IC
Mesoporous MnO/C−N Nanostructures Derived from a Metal−
Organic Framework as High-Performance Anode for Lithium-Ion
Battery
Ji-Liang Niu,† Gui-Xia Hao,‡ Jia Lin,† Xiao-Bin He,† Palanivel Sathishkumar,§ Xiao-Ming Lin,*,†,§
and Yue-Peng Cai*,†
†Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, School of Chemistry and Environment, South China
Normal University, Guangzhou 510006, P. R. China
‡College of Chemistry and Environmental Engineering, Hanshan Normal University, Chaozhou, Guangdong 521041, P. R. China
§Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South
China Normal University, Guangzhou 510006, P. R. China
S
* Supporting Information
ABSTRACT: By application of newly designed ligand 5-(3-(pyridin-3-
yl)benzamido)isophthalic acid (H2PBI) to react with Mn(NO3)2 under
solvothermal conditions, a 2-fold interpenetrated Mn-based metal−
organic framework (Mn-PBI) with rutile-type topology has been obtained.
When treated as a precursor by pyrolysis of Mn-PBI at 500 °C,
mesoporous MnO/C−N nanostructures were prepared and treated as an
lithium-ion battery anode. The MnO/C−N manifests good capacity of
approximately 1085 mAh g−1 after 100 cycles together with superior cyclic
stability and remarkable rate capacity, which is supposed to benefit from a
large accessible specific area and unique nanostructures. The remarkable
performances suggest promising application as an advanced anode
material.
dopant concentration into the networks can introduce more
defects to improve the electrochemical properties in the
application of LIBs.13
1. INTRODUCTION
Nowadays, lithium-ion batteries (LIBs) have been highly
attractive for large-scale applications of electrical and hybrid
electrical vehicles on account of their efficacy in high energy
density, long cycle life, high specific capacity, high operating
voltage, and no memory effect.1 Previously, graphite,2 metal,3
metal oxide,4 and organic electrode materials5 have been
intensively investigated and used for batteries. However, their
large-scale applications and further development have been
impeded due to certain limitations, including cell failure and
poor capacity retention.6 Moreover, small organic molecules
have the drawbacks of low thermal stability and solubility in
organic electrolytes in comparison to those of inorganic
molecules.7 These limitations are still long-term challenging
issues in the development of appropriate electrode materials for
LIBs. Generally speaking, three strategies could be undertaken
to solve these obstacles. First, nanostructured materials can
offer a continuous electron pathway and greatly shorten the
length of charge diffusion, which is crucial to rate capability. For
example, nanotubes,8 nanowires,9 nanoplates,10 nanospheres,11
and core/shell structures12 show remarkable electrochemical
performance due to their unique nanoarchitectures. Second,
porous characteristics and large surface area can provide more
reaction sites and enlarge contact areas between the electrolyte
and active materials. Third, incorporation of the optimized N-
Metal−organic frameworks (MOFs), as a functional family of
inorganic/organic hybrid materials with high porosity and large
surface area, have shown great promise for their applications as
new electrode materials for LIBs.14 The increasing amount of
research demonstrates that MOFs could be successfully
employed as effective sacrificial templates or precursors to
fabricate metal oxides with an excellent lithium storage property
through a high-temperature calcination process.15 In particular,
metal oxides derived from MOFs can be size- and shape-
controlled by adjusting the preparation conditions. For
example, porous MoO2 nano-octahedrons,16 spherical-shaped
CuO nanoparticles,17 urchin-like Mn3O4 microspheres,18
hollow Co3O4 parallelepipeds,19 hierarchical porous anatase
TiO2,20 spindle-like mesoporous α-Fe2O3,21 and so forth were
fabricated using suitable MOFs as templates and displayed
excellent electrochemical performances. Inspired by these great
achievements received to date, the present work mainly focuses
on controlling the morphology of the MOF-derived metal
oxide and further development as advanced anode materials. In
Received: June 11, 2017
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b01486
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this work, a novel ligand, 5-(3-(pyridin-3-yl)benzamido)-
isophthalic acid (H2PBI, Scheme S1) was designed and
synthesized using isophthalate and pyridine as terminal groups,
connected through amide bonds, to construct a porous Mn-
based MOF with 2-fold interpenetrated rutile topology. Direct
pyrolysis of this MOF gave rise to mesoporous MnO/C−N
nanostructures, which could be used as an LIB anode with
improved reversible capacity and excellent cyclability.
manganese nitrate in a mixture of DMF−C2H5OH at 80 °C for
72 h. Mn-PBI possesses a 2-fold interpenetrated (3,6)-
connected three-dimensional (3D) structure. As depicted in
Figure 1a, each Mn(II) coordinates with four oxygen atoms
2. EXPERIMENTAL SECTION
2.1. Materials Characterization. Functional groups of the
materials were assessed using Fourier transform infrared spectroscopy
(Thermo Nicolet NEXUS 670 FT-IR, USA). Elemental analyses were
carried out using an elemental analyzer (PerkinElmer 240, USA).
Crystalline phase was identified by a Bruker D8 Advance X-ray
diffraction pattern diffractometer (BRUKER-AXS, Germany). Raman
spectra were obtained from a Renishaw inVia confocal Raman
microscope (UK). Netzsch Thermo Microbalance TG 209 F1 Libra
(Germany) was used for thermogravimetric analyses (TGA) to
determine the thermal behavior (mass) of the material. The sorption
isotherms were assessed using a Belsorp max gas sorption analyzer
(Japan) at 77 K. X-ray photoelectron spectroscopy (XPS) was
recorded by ESCALAB 250Xi XPS spectrometer (USA). The surface
morphology and architecture were recorded by scanning electron
microscopy (SEM, TESCAN Maia 3, Czech) and transmission
electron microscopy (TEM, JEM-2100HR, Japan). A Varian Mercury
Figure 1. Mn-PBI: (a) Coordination environment of Mn(II), (b) 3D
structure with space filling, (c) 2-fold interpenetrated structure, and
(d) schematic representation of the self-interpenetrated (3,6)-
connected rutile topology. All hydrogen atoms are omitted for clarity.
1
Plus 300 MHz spectrometer was used to record H NMR spectra
(USA).
2.2. Preparation of the Mn-PBI MOF. The synthetic route of the
H2PBI ligand is given in Scheme S1, and the obtained ligand was
further confirmed by its H1 NMR spectrum (Figure S1). To a mixed
solvent of dimethylformamide (DMF, 3 mL) and ethanol (3 mL) in a
20 mL scintillation vial were added H2PBI (18 mg, 0.05 mmol) and
Mn(NO3)2·4H2O (25 mg, 0.1 mmol). The capped vial was heated at
80 °C at a rate of 0.5 °C/min for 32 h. After cooling, pale pink crystals
of Mn-PBI were obtained (yield: 75.3%) by filtration. IR: 3519, 3453,
1650, 1564, 1423, 1373, 1318, 774, 723 cm−1 (see Figure S3).
Elemental analysis (% calcd/found): C, 56.57/56.59; N, 8.60/8.57; H,
3.92/3.91.
2.3. Electrochemical Measurements. The MnO/C−N elec-
trode was prepared by annealing of Mn-PBI MOF as templates at 500
°C for 3 h under a N2 atmosphere. Electrochemical behavior of MnO/
C−N electrode was assessed by coin-type half cells (2025 type)
separated by a celgard 2400 membrane. LiPF6 (1 M) was dissolved in
diethyl carbonate and ethylene carbonate in a volume ratio of 1:1 as
electrolyte. The mixture of active material, polyvinylidene fluoride
(PVDF), and super P carbon black binder in the ratio of 7:1:2 (w/w)
was coated onto a piece of copper foil and then was placed in an oven
at 70 °C for 1 day. LAND CT2001A multichannel battery testing
system was applied to detect the galvanostatic charge/discharge
between 0.01 and 3.0 V. The cyclic voltammetry (CV) measurements
were scanned at 0.05 mV s−1 from 0.01 to 3.0 V with an
Electrochemical Workstation (CHI660C) .
(O1, O3A, O4A, and O2B), one nitrogen (N1C) from four
different PBI ligands, and one coordinated DMF molecule to
furnish a distorted octahedral geometry. The Mn−O bond
lengths are in the range of 2.092(3)−2.315(5) Å, which are
comparable to the expected values for Mn(II)−O in the
previous reports.23,24
Two adjacent Mn ions are connected between the
isophthalate groups, generating a 1D linear chain with binuclear
[Mn2(COO)4] units (Figure S4). Moreover, each PBI ligand
employs its one pyridyl and two carboxylate groups in turn to
link another four metal atoms, generating a 3D framework with
1D rectangular channel (Figure 1b). It is worth mentioning that
one 3D net combines with another identical one, leading to the
formation of a self-interpenetrated structure (Figure 1c). A
similar 2-fold interpenetrated network can be observed in
previous literature.25,26 After omitting the DMF molecules,
PLATON27 analysis indicates that solvent accessible volume is
23.3% per unit cell volume [489.6/2097.3 Å3]. If each PBI2−
ligand serves as a three-connector and each Mn(II) acts as a
three-connecting node, then Mn-PBI represents a 2-fold
2.4. X-ray Crystallographic Studies. X-ray reflection intensities
were performed with a Bruker APEX II diffractometer at 296 K using
graphite monochromatic Mo Kα radiation (λ = 0.71073 Å). The
empirical absorption corrections were used to correct the reflections,
and the structure was refined by full-matrix least-squares on F2 using
the SHELXL programs (SHELXTL-2014).22 The isotropic displace-
ment parameter was used to place the organic hydrogen atoms in
calculated positions. The details of the crystal parameters and
refinement are presented in Table S1. Table S2 presents the selected
bond lengths and angles. CCDC 1534095 contains the crystallographic
data.
interpenetrated (3,6)-connected rutile net with the Schlafli
̈
symbol of (42·610·83) (4·62)2 simplified by TOPOS (Figure
1d).28
The morphology of Mn-PBI particles was observed by SEM
analysis. The surfaces of the Mn-PBI MOFs are smooth and
have cubic-like shape with the sizes of tens of microns (Figure
S6). The powder X-ray diffraction (PXRD) pattern shows that
most diffraction peaks are well matched with the simulated
pattern results, confirming the phase purity of the bulk sample
(Figure S7). The TG curve shows that an initial loss (15.3%)
was observed within 150−300 °C due to the release of a DMF
molecule (calcd 15.0%). The further weight loss between 300
and 500 °C is ascribed to decomposition of the framework
(Figure S8). N2 adsorption/desorption isotherms present
3. RESULTS AND DISCUSSION
3.1. Structure and Characterization of Mn-PBI MOF.
Mn-PBI were successfully prepared by reacting H2PBI with
B
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Figure 2. MnO/C−N electrode: (a) XRD, (b) Raman spectrum, (c) XPS spectrum, and (d) N2 adsorption−desorption isotherms with inset pore-
size distribution.
typical type-I microporous characteristics with a surface area of
525 m2 g−1 (Figure S9). According to the TGA result, Mn-BPI
samples in our case were calcined at 500 °C by one-step
thermal treatment under a flow of air to ensure complete
conversion of precursors to the final products.
type N atoms).35 Peaks at 530.1 and 531.6 eV correspond to
the O in Mn−O and C−O, respectively.36 On the basis of XPS
analysis, the elemental contents of C and N were 12.18 and
5.10 wt %, respectively. N2 adsorption−desorption isotherms
were measured to evaluate the porosity of Mn/C−N
composites. Figure 2d exhibits clear type IV with hysteresis
loops, indicating the mesoporous characteristics (IUPAC
classification). The Barrett−Joyner−Halenda (BJH) method
was applied to calculate the pore-size distribution. The result
shows the existence of two kinds of mesopores with sizes of 13
and 26 nm. The Brunauer−Emmett−Teller (BET) result
confirms the surface area is 146.4 m2 g−1 and the pore volume is
0.59 cm3 g−1. This mesoporous structure and large surface not
only provides a convenient pathway to electrolyte diffusion and
Li-ion transfer but also facilitates accommodating the
volumetric variations during the lithium storage process,
which is highly favorable for the electrochemical performance
enhancement as electrode.
For better observation of the morphology and architecture of
the Mn/C−N composite, SEM and TEM were applied.
Compared to the Mn-MOF precursor, the shape of MnO/
C−N was retained well, whereas the size slightly shrinks
ranging from 5 to 10 μm due to decomposition and volume
contraction after calcination (Figure 3a). The surface becomes
relatively rough, and many tiny nanoparticles can be clearly
observed on the surface (Figure 3b). The surface of the
material was decorated with many holes due to the formation of
pores during the thermal treatment (Figure 3c). The TEM
image in Figure 3d further confirms its nanoparticles with size
of less than 20 nm. The interplanar lattice fringe distance is
found to be 0.26 nm depicted in the high-resolution TEM
3.2. Characterization of the MnO/C−N Materials. XRD
analysis in Figure 2a confirmed that the obtained product after
pyrolysis was composed of monoclinic cubic structure space
group Fm3m of MnO phase (JCPDS No.07-0230). Raman
spectrum reveals two weak bands at 550 and 644 cm−1 are
indexed to the typical characteristic of the MnO (Figure
2b).29,30 Obviously, two other broad peaks at 1357 cm−1 for D-
bond (disordered carbon) and 1597 cm−1 for G-bond (ordered
graphitic carbon) are also detected simultaneously.31 In
addition, the intensity of the G peak is greatly enhanced
compared to that of the D peak with a high IG/ID band
intensity ratio of ∼1.20, which suggests the greatly increased
graphitization degree of the carbon for the final samples.32 For
the chemical state and composition to be examined further, X-
ray photoelectron spectroscopy (XPS) spectra were recorded.
The characteristic peaks of C 1s, N 1s, O 1s, and Mn (2s, 2p,
3s, and 3p) were observed in a wide scan spectrum in Figure 2c,
further confirming the successful synthesis of MnO/C−N. Two
major peaks at 641.3 and 652.9 eV are detected in the high-
resolution XPS of Mn(II) 2p (Figure S10), corresponding to
Mn 2p3/2 and Mn 2p1/2, respectively. These results are well
matched with MnO.33 The C 1s XPS peaks can be fitted into
four parts at 284.6 eV (C−C), 285.6 eV (C−O), 286.3 eV
(CO), and 288.4 eV (OC−O), respectively.34 The N 1s
spectrum shows three components at 399.1 eV (pyridinic (N-
6)), 400.9 eV (pyrrolic (N-5)), and 401.5 eV (graphitic (N-Q)
C
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was recorded to examine valence states of manganese after the
first charge process. As shown in Figure S11, after a peak fitting
deconvolution, the species of Mn4+ (644.1 eV), Mn3+ (642.9
eV), and Mn2+ (641.2 eV) could be observed, which indicates
the presence of Mn4+ and Mn3+ valence states in the electrode
after the first charge, further accounting for the appearance of a
peak at 1.77 V in the CV curves. The subsequent CV curves
become stable and overlap, indicative of good reversibility.
Figure 4b demonstrates the galvanostatic charge/discharge
within 0.01−3.0 V at 300 mA g−1. In the first discharge process,
it clearly shows that a distinct long voltage plateau was found
around 0.2 V, which can be assigned to the reduction of Mn2+
to Mn0. The discharge plateau increases to 0.5 V in the second
cycle, arising from the formation of Li2O and Mn (irreversible
structural transformation). The MnO/C−N composite elec-
trode delivers approximately 1507 mAh g−1 as the first
discharge capacity and 1143 mAh g−1 as the charge capacity.
The initial loss of capacity with a Coulombic efficiency of 75.8%
might be due to the inevitable decomposition of the electrolyte
and SEI layer, which is regarded as an irreversible electro-
chemical reaction. Despite the initial capacity loss, the charge−
discharge profiles are basically invariable without capacity
fading from the subsequent cycles. Interestingly, a discharge
capacity of 1085 mAh g−1 was retained after the 100th cycling
(Figure 4c). Meanwhile, Coulombic efficiency maintained
almost 100% after initial cycles, which confirms the reusability
of the MnO/C−N composite electrode. Figure 4d illustrates
the rate capacities of the MnO/C−N electrode. When the
current densities rise from 0.3 to 0.5, 1, 2, and 3 A g−1, the
capacity decreased from 1085 to 924, 877, 775, and 665 mAh
g−1, respectively. Surprisingly, even at a high current density of
5 A g−1, a high capacity of 552 mA h g−1 was still retained. In
addition, when the current density was restored to 0.3 A g−1,
the fabricated electrode almost recovered its original capacity,
which proved the excellent rate capability. This observed
excellent capacity is considerably higher than that of MnO with
a theoretical value of 765 mAh g−1 and other MnO hybrid
anode materials reported previously (Table S3). Moreover, in
comparison with other MOF-derived porous MnO materials,
our Mn/C−N electrode shows competitive reversible capacity
and more superior rate capacity. In particular, it delivers a
capacity of up to 665 mAh g−1 even at 5 A g−1, proving long-
term cycling stability and also incomparable high-rate perform-
ance.
Calcination temperature is also one of the important
parameters to obtain preferred electrode materials while using
MOFs as sacrificial templates. For comparison, Mn-PBI MOFs
were calcined at different temperatures. The similar PXRD
patterns confirm the cubic MnO phase after the thermal
transformation process (Figure S12). Apparently, the obtained
Mn/C−N electrode material calcined at 500 °C exhibits the
highest discharge capacity compared with the materials
pyrolyzed at 600 and 700 °C (Figure 5a). From the SEM
images in Figure S13, some of the final products were found to
collapse at 600 °C. Moreover, the initial morphology totally
disappeared, and some agglomerates with nonregular shape
were obtained at a higher temperature (700 °C). Thus, it is
highly essential to control the heating temperature for the
conversion of the Mn-PBI MOF template into the desired
architecture. As demonstrated in previous literature, the
amount of N-doping composition could improve lithium
storage capacity.47,48 The N content of MnO/C−N-500
(5.10 wt %) is larger than that of MnO/C−N-600 (4.29 wt
Figure 3. MnO/C−N composite: (a, b) low- and (c) high-
magnification SEM images, (d) TEM and (e) HRTEM images with
selected-area electron diffraction pattern, and (f) EDS mapping
images.
(HRTEM) image (Figure 3e), which is indexed to the (111)
lattice plane of cubic MnO. Selected-area electron diffraction
(SAED) pattern (inset in Figure 3e) clearly shows a well-
defined crystalline structure. Additionally, energy-dispersive
spectroscopy (EDS) element mapping images further reveal the
presence of O, N, C, and Mn elements (Figure 3f) in
agreement with the XPS analysis.
3.3. Electrochemical Analysis. The MnO/C−N electrode
exhibited excellent lithium storage performance when evaluated
as an anode for LIBs. CV curves were scanned at a rate of 0.05
mV s−1. As depicted in Figure 4a, three reduction peaks were
observed in the first cathodic sweep. The sharp peak appearing
at 0.16 V results from the reduction of Mn2+ to Mn0.37,38 The
reaction can be described as follows: MnO + 2Li+ + 2e− → Mn
+ Li2O. However, this peak shifted to approximately 0.2 V in
the second cycle, which is ascribed to the Li2O and metallic
manganese formation, indicating an irreversible phase trans-
formation.39 A small reduction peak was detected at 0.61 V and
then disappeared after subsequent cycles, which indicates the
generation of a solid electrolyte interface (SEI) layer with
irreversible reduction of electrolyte.40,41 A reduction peak near
0.84 V corresponds to the reduction of Mn3+/Mn4+ to Mn2+.
The oxidation peak appearing at 1.01 V in the anodic scan
performance is due to the oxidation reaction of Mn0 to Mn2+
(Mn + Li2O → MnO + 2Li+ + 2e−),42,43 which remained after
further cycling. In the meantime, one weak peak located at 1.77
V was also detected, which can originate from the reoxidation
of Mn(II) to a higher oxidation state.44−46 The XPS spectrum
D
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Figure 4. MnO/C−N electrode: (a) CV curves, (b) voltage profile at 300 mA g−1 ranging from 0.01 and 3.0 V, (c) cycle performance and
Coulombic efficiency curves, and (d) rate performance at different current densities.
Figure 5. Mn-PBI MOFs pyrolyzed at different temperatures: (a) cycle-life performances at 0.3 A g−1 and (b) Nyquist plots for the three electrode
materials.
%) and MnO/C−N-700 (4.04 wt %). Specifically, the total
pyrrolic (N-5) and pyridinic (N-6) N atoms are as much as 75
at % in the MnO/C−N-500 samples (Figure S14 and Table
S4), making the structure electron deficient, which can more
strongly bind lithium atoms and accept more charge from Li
ions.49,50 Electrochemical impedance spectra were also carried
out (Figure 5b). In the region of high-to-medium frequencies,
there is a depressed semicircle for all of the curves associated
with charge-transfer resistance (Rct) between electrolyte and
electrode. A sloping line in the low frequency region can be
found, which is related to diffusion of lithium inside the
electrode (Warburg diffusion resistance, Rw). Evidently, the
porous MnO/C−N after thermal treatment at 500 °C shows
smaller Rct compared to those of the other two materials
obtained at 600 and 700 °C, suggesting better charge transfer
kinetics.51 These results also proved the superior electro-
chemical performance of MnO/C−N obtained at 500 °C.
4. CONCLUSIONS
In summary, a 2-fold interpenetrated MOF with (3,6)-
connected rutile topology was obtained by application of a
new ligand to assemble with Mn(II) ions. Mesoporous Mn/C−
N was successfully prepared through calciantion of the title
MOF as a precursor. The resultant Mn/C−N nanoparticles
delivered a high capacity of 1085 mAh g−1 together with
superior cyclic stability and good rate capacity. The improved
lithium storage is supposed to benefit from the large accessible
specific area and unique nanostructures. The remarkable
performance makes it a promising LIB anode.
E
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Ramakrishna, S.; Chowdari, B. V. R. Electrospun α-Fe2O3 Nanorods as
a Stable, High Capacity Anode Material for Li-ion Batteries. J. Mater.
Chem. 2012, 22, 12198−12204.
(8) Huang, G.; Zhang, F.; Zhang, L.; Du, X.; Wang, J.; Wang, L.
Hierarchical NiFe2O4/Fe2O3 nanotubes derived from metal organic
frameworks for superior lithium ion battery anodes. J. Mater. Chem. A
2014, 2, 8048−8053.
(9) Liu, B.; Zhang, J.; Wang, X.; Chen, G.; Chen, D.; Zhou, C.; Shen,
G. Hierarchical Three-Dimensional ZnCo2O4 Nanowire Arrays/
Carbon Cloth Anodes for a Novel Class of High-Performance Flexible
Lithium-Ion Batteries. Nano Lett. 2012, 12, 3005−3011.
(10) Zhao, J.; Wang, F.; Su, P.; Li, M.; Chen, J.; Yang, Q.; Li, C.
Spinel ZnMn2O4 Nanoplate Assemblies Fabricated Via “Escape-By-
Crafty-Scheme” Strategy. J. Mater. Chem. 2012, 22, 13328−13333.
(11) Gao, X. J.; Wang, J. W.; Zhang, D.; Nie, K. Q.; Ma, Y. Y.; Zhong,
J.; Sun, X. H. Hollow NiFe2O4 Nanospheres on Carbon Nanorods as a
Highly Efficient Anode Material for Lithium ion Batteries. J. Mater.
Chem. A 2017, 5, 5007−5012.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b01486.
■
S
Experimental details, XRD patterns, TGA curve, XPS
spectrum, and SEM images, and crystallographic data
(PDF)
Accession Codes
CCDC 1534095 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_
request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: +44 1223 336033.
(12) Shao, J.; Wan, Z.; Liu, H.; Zheng, H.; Gao, T.; Shen, M.; Qu, Q.;
Zheng, H. Metal Organic Frameworks-Derived Co3O4 Hollow
Dodecahedrons with Controllable Interiors as Outstanding Anodes
for Li Storage. J. Mater. Chem. A 2014, 2, 12194−12200.
(13) Yang, Y.; Jin, S.; Zhang, Z.; Du, Z.; Liu, H.; Yang, J.; Xu, H.; Ji,
H. Atomic Layer Deposition Alumina-Passivated Silicon Nanowires:
Probing the Transition from Electrochemical Double-Layer Capacitor
to Electrolytic Capacitor. ACS Appl. Mater. Interfaces 2017, 9, 14180−
14186.
(14) Maiti, S.; Pramanik, A.; Manju, U.; Mahanty, S. Reversible
Lithium Storage in Manganese 1,3,5-Benzenetricarboxylate Metal−
Organic Framework with High Capacity and Rate Performance. ACS
Appl. Mater. Interfaces 2015, 7, 16357−16363.
(15) Hu, L.; Chen, Q. Hollow/Porous Nanostructures Derived from
Nanoscale Metal−Organic Frameworks Towards High Performance
Anodes for Lithium-ion Batteries. Nanoscale 2014, 6, 1236−1257.
(16) Xia, G.; Liu, D.; Zheng, F.; Yang, Y.; Su, J.; Chen, Q.
Preparation of Porous MoO2@C Nano-Octahedrons from a
Polyoxometalate-based Metal−Organic Framework for Highly Rever-
sible Lithium Storage. J. Mater. Chem. A 2016, 4, 12434−12441.
(17) Banerjee, A.; Singh, U.; Aravindan, V.; Srinivasan, M.; Ogale, S.
Synthesis of CuO Nanostructures from Cu-based Metal Organic
Framework (MOF-199) for Application as Anode for Li-ion Batteries.
Nano Energy 2013, 2, 1158−1163.
(18) Huang, S.-Z.; Cai, Y.; Jin, J.; Liu, J.; Li, Y.; Yu, Y.; Wang, H.-E.;
Chen, L.-H.; Su, B.-L. Hierarchical Mesoporous Urchin-like Mn3O4/
carbon Microspheres with Highly Enhanced Lithium Battery Perform-
ance by in-situ Carbonization of New Lamellar Manganese Alkoxide
(Mn-DEG). Nano Energy 2015, 12, 833−844.
(19) Han, Y.; Zhao, M. L.; Dong, L.; Feng, J. M.; Wang, Y. J.; Li, D.
J.; Li, X. F. MOF-Derived Porous Hollow Co3O4 Parallelepipeds for
Building High-Performance Li-ion Batteries. J. Mater. Chem. A 2015, 3,
22542−22546.
(20) Wang, Z.; Li, X.; Xu, H.; Yang, Y.; Cui, Y.; Pan, H.; Wang, Z.;
Chen, B.; Qian, G. Porous Anatase TiO2 Constructed from a Metal−
Organic Framework for Advanced Lithium-ion Battery Anodes. J.
Mater. Chem. A 2014, 2, 12571.
(21) Xu, X.; Cao, R.; Jeong, S.; Cho, J. Spindle-like Mesoporous α-
Fe2O3 Anode Material Prepared from MOF Template for High-Rate
Lithium Batteries. Nano Lett. 2012, 12, 4988−4991.
(22) Sheldrick, G. M. SHELXT−Integrated space-group and crystal-
structure determination. Acta Crystallogr., Sect. A: Found. Adv. 2015,
71, 3−8.
AUTHOR INFORMATION
■
Corresponding Authors
*E-mail: linxm@scnu.edu.cn.
*E-mail: caiyp@scnu.edu.cn.
ORCID
Xiao-Ming Lin: 0000-0001-8835-103X
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge financial support from the National
Natural Science Foundation of China (Grants 21401059 and
21471061), Applied Science and Technology Planning Project
of Guangdong Province (2017A010104015 and
2015B010135009), Innovation Team Project of Guangdong
Ordinary University (2015KCXTD005), the Great Scientific
Research Project of Guangdong Ordinary University
(2016KZDXM023), the Innovation Project of Graduate School
of South China Normal University, and Special Funds for the
Cultivation of Guangdong College Students’ Scientific and
Technological Innovation (“Climbing Program” Special
Funds).
REFERENCES
■
(1) Reddy, M. V.; Subba Rao, G. V.; Chowdari, B. V. R. Metal Oxides
and Oxysalts as Anode Materials for Li Ion Batteries. Chem. Rev. 2013,
113, 5364−5457.
(2) Zhang, L.; Wu, H. B.; Madhavi, S.; Hng, H. H.; Lou, X. W.
Formation of Fe2O3 Microboxes with Hierarchical Shell Structures
from Metal-Organic Frameworks and Their Lithium Storage Proper-
ties. J. Am. Chem. Soc. 2012, 134, 17388−17391.
(3) Jang, B.; Park, M.; Chae, O. B.; Park, S.; Kim, Y.; Oh, S. M.; Piao,
Y.; Hyeon, T. Direct Synthesis of Self-Assembled Ferrite/Carbon
Hybrid Nanosheets for High Performance Lithium-Ion Battery
Anodes. J. Am. Chem. Soc. 2012, 134, 15010−15015.
(4) Zhou, L.; Xu, H.; Zhang, H.; Yang, J.; Hartono, S. B.; Qian, K.;
Zou, J.; Yu, C. Cheap and Scalable Synthesis of α-Fe2O3 Multi-Shelled
Hollow Spheres as High-Performance Anode Materials for Lithium
ionBatteries. Chem. Commun. 2013, 49, 8695−8697.
(5) Liu, H.; Wexler, D.; Wang, G. One-Pot Facile Synthesis of Iron
Oxide Nanowires as Hhigh Capacity Anode Materials for Lithium Ion
Batteries. J. Alloys Compd. 2009, 487, 24−27.
(6) Palacín, M. R. Recent Advances in Rechargeable Battery
Materials: a Chemist’s Perspective. Chem. Soc. Rev. 2009, 38, 2565−
2575.
(23) Deng, Y.-K.; Su, H.-F.; Xu, J.-H.; Wang, W.-G.; Kurmoo, M.;
Lin, S.-C.; Tan, Y.-Z.; Jia, J.; Sun, D.; Zheng, L.-S. Hierarchical
assembly of a {MnII15MnIII4} Brucite Disc: Step-by-Step Formation
and Ferrimagnetism. J. Am. Chem. Soc. 2016, 138, 1328−1334.
̌ ́
(24) Yang, F.; Deng, Y.-K.; Guo, L.-Y.; Su, H.-F; Jaglicic, Z.; Feng, Z.-
Y.; Zhuang, G.-L.; Zeng, S.-Y.; Sun, D. Structural, electrochemical and
magnetic analyses of a new octanuclear MnIII2MnII6 cluster with linked-
defect cubane topology. CrystEngComm 2016, 18, 1329−1336.
(7) Cherian, C. T.; Sundaramurthy, J.; Kalaivani, M.; Ragupathy, P.;
Kumar, P. S.; Thavasi, V.; Reddy, M. V.; Sow, C. H.; Mhaisalkar, S. G.;
F
DOI: 10.1021/acs.inorgchem.7b01486
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(25) Chen, W.-M.; Meng, X.-L.; Zhuang, G.-L.; Wang, Z.; Kurmoo,
M.; Zhao, Q.-Q.; Wang, X.-P.; Shan, B.; Tung, C.-H.; Sun, D. A
reduced Graphene Oxide Composites Derived from Graphene Oxide
Plus the Transformation of Mn(VI) to Mn(II) by the ReducingPower
of Graphene Oxide. J. Mater. Chem. A 2015, 3, 297−303.
(43) Li, C. C.; Yu, H.; Yan, Q.; Hng, H. H. Nitrogen Doped Carbon
Nanotubes Encapsulated MnO Nanoparticles Derived from Metal
Coordination Polymer Towards High Performance Lithium-ion
Battery Anodes. Electrochim. Acta 2016, 187, 406−412.
(44) Tang, X.; Sui, G.; Cai, Q.; Zhong, W.; Yang, X. Novel MnO/
Carbon Composite Anode Material with Multi-modal Pore Structure
for High Performance Lithium-ion Batteries. J. Mater. Chem. A 2016,
4, 2082−2088.
(45) Guo, J.; Liu, Q.; Wang, C.; Zachariah, M. R. Interdispersed
Amorphous MnOx-Carbon Nanocomposites with Superior Electro-
chemical Performance as Lithium-Storage Material. Adv. Funct. Mater.
2012, 22, 803−811.
(46) Zhao, G.; Huang, X.; Wang, X.; Connor, P.; Li, J. Synthesis and
lithium-storage Properties of MnO/reduced Graphene Oxide
Composites Derived from Graphene Oxide Plus the Transformation
of Mn(VI) to Mn(II) by the Reducing Power of Graphene Oxide. J.
Mater. Chem. A 2015, 3, 297−303.
(47) Qie, L.; Chen, W.-M.; Wang, Z.-H.; Shao, Q.-G.; Li, X.; Yuan,
L.-X.; Hu, X.-L.; Zhang, W.-X.; Huang, Y.-H. Nitrogen-Doped Porous
Carbon Nanofiber Webs as Anodes for Lithium Ion Batteries with a
Superhigh Capacity and Rate Capability. Adv. Mater. 2012, 24, 2047−
2050.
(48) Wang, Z.; Xiong, X.; Qie, L.; Huang, Y. High-performance
lithium storage in nitrogen-enriched carbon nanofiber webs derived
from polypyrrole. Electrochim. Acta 2013, 106, 320−326.
(49) Mao, Y.; Duan, H.; Xu, B.; Zhang, L.; Hu, Y.; Zhao, C.; Wang,
Z.; Chen, L.; Yang, Y. Lithium storage in nitrogen-rich mesoporous
carbon materials. Energy Environ. Sci. 2012, 5, 7950−7955.
(50) Ma, C.; Shao, X.; Cao, D. Nitrogen-doped graphene nanosheets
as anode materials for lithium ion batteries: a first-principles study. J.
Mater. Chem. 2012, 22, 8911−8915.
2+
superior fluorescent sensor for Al3+ and UO2 based on a Co(II)
metal−organic framework with exposed pyrimidyl Lewis base sites. J.
Mater. Chem. A 2017, 5, 13079−13085.
(26) Wang, X. P.; Chen, W. M.; Qi, H.; Li, X. Y.; Rajnak, C.; Feng, Z.
Y.; Kurmoo, M.; Boca, R.; Jia, C. J.; Tung, C.-H.; Sun, D. Solvent-
controlled phase transition of a CoII-organic framework: From achiral
to chiral and two to three Dimensions. Chem. - Eur. J. 2017, 23, 7990−
7996.
(27) Spek, A. L. Crystal Structure Refinement with SHELXL. Acta
Crystallogr., Sect. C: Struct. Chem. 2015, 71, 9−18.
(28) Blatov, V. A.; Shevchenko, A. P.; Proserpio, D. M. Applied
Topological Analysis of Crystal Structures with the Program Package
ToposPro. Cryst. Growth Des. 2014, 14, 3576−3586.
(29) Zhu, W.; Huang, H.; Zhang, W.; Tao, X.; Gan, Y.; Xia, Y.; Yang,
H.; Guo, X. Synthesis of MnO/C Composites Derived from Pollen
Template for Advanced Lithium-ion Batteries. Electrochim. Acta 2015,
152, 286−293.
(30) Sun, D.; Tang, Y.; Ye, D.; Yan, J.; Zhou, H.; Wang, H. Tuning
the Morphologies of MnO/C Hybrids by Space Constraint Assembly
of Mn-MOFs for High Performance Li Ion Batteries. ACS Appl. Mater.
Interfaces 2017, 9, 5254−5262.
(31) Han, X.; Chen, W.-M.; Han, X.; Tan, Y.-Z.; Sun, D.; Nitrogen-
rich, M. O. F. Derived Porous Co3O4/N−C Composites with Superior
Performance in Lithium-ion Batteries. J. Mater. Chem. A 2016, 4,
13040−13045.
(32) Chen, Y.; Li, X.; Park, K.; Song, J.; Hong, J.; Zhou, L.; Mai, Y.
W.; Huang, H.; Goodenough, J. B. Hollow Carbon-Nanotube/
Carbon-Nanofiber Hybrid Anodes for Li-Ion Batteries. J. Am. Chem.
Soc. 2013, 135, 16280−16283.
(33) Zheng, F.; Xia, G.; Yang, Y.; Chen, Q. MOF-derived Ultrafine
MnO Nanocrystals Embedded in a Porous Carbon Matrix as High-
Performance Anodes for Lithium-ion Batteries. Nanoscale 2015, 7,
9637−9645.
(51) Bai, Z.; Zhang, Y.; Zhang, Y.; Guo, C.; Tang, B.; Sun, D. MOFs-
Derived Porous Mn2O3 as High-performance Anode Material for Li-
ion battery. J. Mater. Chem. A 2015, 3, 5266−5269.
(34) Wang, S.; Chen, M.; Xie, Y.; Fan, Y.; Wang, D.; Jiang, J.-J.; Li,
Y.; Grutzmacher, H.; Su, C.-Y. Nanoparticle Cookies Derived from
̈
Metal-Organic Frameworks: Controlled Synthesis and Application in
Anode Materials for Lithium-Ion Batteries. Small 2016, 12, 2365−
2375.
(35) Sun, D.; Tang, Y.; Ye, D.; Yan, J.; Zhou, H.; Wang, H. Tuning
the Morphologies of MnO/C Hybrids by Space Constraint Assembly
of Mn-MOFs for High Performance Li Ion Batteries. ACS Appl. Mater.
Interfaces 2017, 9, 5254−5262.
(36) Lin, X.-M.; Niu, J.-L.; Lin, J.; Wei, L.-M.; Hu, L.; Zhang, G.; Cai,
Y.-P. Lithium-Ion-Battery Anode Materials with Improved Capacity
from a Metal-Organic Framework. Inorg. Chem. 2016, 55, 8244−8247.
(37) Xiao, Y.; Wang, X.; Wang, W.; Zhao, D.; Cao, M. Engineering
Hybrid between MnO and N-Doped Carbon to Achieve Exceptionally
High Capacity for Lithium-Ion Battery Anode. ACS Appl. Mater.
Interfaces 2014, 6, 2051−2058.
(38) Zhang, K.; Han, P.; Gu, L.; Zhang, L.; Liu, Z.; Kong, Q.; Zhang,
C.; Dong, S.; Zhang, Z.; Yao, J.; Xu, H.; Cui, G.; Chen, L. Synthesis of
Nitrogen-Doped MnO/Graphene Nanosheets Hybrid Material for
Lithium Ion Batteries. ACS Appl. Mater. Interfaces 2012, 4, 658−664.
(39) Guo, S. M.; Lu, G. X.; Qiu, S.; Liu, J. R.; Wang, X. Z.; He, C. Z.;
Wei, H. G.; Yan, X. R.; Guo, Z. H. Carbon-coated MnO
Microparticulate Porous Nanocomposites Serving as Anode Materials
with Enhanced Electrochemical Performances. Nano Energy 2014, 9,
41−49.
(40) Sun, Y. M.; Hu, X.; Luo, W.; Xia, F. F.; Huang, Y. H.
Reconstruction of Conformal Nanoscale MnO on Graphene as a
High-Capacity and Long-Life Anode Material for Lithium Ion
Batteries. Adv. Funct. Mater. 2013, 23, 2436−2444.
(41) Sun, B.; Chen, Z.; Kim, H.-S.; Ahn, H.; Wang, G. MnO/C
Core−shell Nanorods as High Capacity Anode Materials for Lithium-
ion Batteries. J. Power Sources 2011, 196, 3346−3349.
(42) Zhao, G.; Huang, X.; Wang, X.; Connor, P.; Li, J.; Zhang, S.;
Irvine, J. T. S. Synthesis and Lithium-storage Properties of MnO/
G
DOI: 10.1021/acs.inorgchem.7b01486
Inorg. Chem. XXXX, XXX, XXX−XXX