Synthesis of Chlorine-Substituted Graphdiyne and Applications for Lithium-Ion Storage

Article abstract of DOI:10.1002/anie.201704779

Chlorine-substituted graphdiyne (Cl-GDY) is prepared through a Glaser–Hay coupling reaction on the copper foil. Cl-GDY is endowed with a unique π-conjugated carbon skeleton with expanded pore size in two dimensions, having graphdiyne-like sp- and sp²

Full text of DOI:10.1002/anie.201704779

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Accepted Article
Title: Synthesis of Chlorine-substituted Graphdiyne and Its Application
for Lithium-ion Storage
Authors: Ning Wang, Jianjiang He, Zeyi Tu, Ze yang, Fuhua Zhao,
Xiaodong Li, Changshui Huang, Kun Wang, Tonggang Jiu,
Yuanping Yi, and Yuliang Li
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201704779
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10.1002/anie.201704779
Angewandte Chemie International Edition
COMMUNICATION
Synthesis of Chlorine-substituted Graphdiyne and Its Application
for Lithium-ion Storage
Ning Wang[a], Jianjiang He[a,b], Zeyi Tu[b,c], Ze Yang[a], Fuhua Zhao[a], Xiaodong Li[a,b], Changshui Huang*[a],
Kun Wang[a], Tonggang Jiu[a], Yuanping Yi[c], and Yuliang Li [c]
Abstract: Herein, chlorine substitutional graphdiyne (Cl-GDY) is
prepared through Glaser-Hay coupling reaction on the copper foil. Cl-
GDY is endowed a unique π-conjugated carbon skeleton with
expanded pore size on two dimensional molecule plane, which also
comprises graphdiyne-like sp- and sp2- hybridized carbon atoms. As
a result, the transfer tunnels for lithium (Li) ions on the perpendicular
direction of the molecular plane are enlarged. Moreover, benefiting
from the bottom-to-up fabrication procedure of graphdiyne and the
strong chemical tailorability of the alkinyl-contained monomer, the
substitutional chlorine atoms with appropriate electronegativity and
atom size are in high content and even distributed on the as-prepared
carbon framework, which will synergistically stabilize the Li
intercalated in the Cl-GDY framework, and thus generate more Li
storage sites. Profiting from the above unique structure, Cl-GDY
shows remarkable electrochemical properties in lithium ion half cells.
carbon material system may tune the molecule pore size and the
conductivity of the carbon material more precisely. For example,
chlorination of Graphene[7], reduced Graphite Oxide[8],
mesoporous carbon[9] has tailored the structure and improve the
performance of original carbon materials, which will widen their
potential application for various purposes such as electrochemical
and electronic devices.[10]
All the previous reports indicate that the carbon materials doped
with hetero atoms has shown remarkable properties, meanwhile,
some drawbacks of doping method are also revealed. Firstly, the
quantity of doped element is hard to be precisely controlled, and
it is usually limited under a maximum value. Secondly, the
distributing position of the hetero atom is uncertain, some of the
doping atoms maybe easier to locate on the edge of the molecular
plane. Thirdly, the intrinsic structure of the carbon material maybe
destroyed in some extent, which will result in the discontinuity of
the conjugation. In order to avoid the above disadvantages, a new
strategy for the incorporation of hetero atom into carbon material
is in urgent need. The successful preparation of graphdiyne film
on copper foil through chemical reaction provides us an excellent
bottom-to-up strategy to prepare new carbon or hetero atom
substituted carbon material.[11] By choosing appropriate
monomers, the pore size in the two-dimensional molecule plane
can be tuned, and the distribution of the hetero-atom induced into
the carbon framework can also be precisely controlled due to the
structure tailorability of the monomers. It can be expected that the
adjustability of the pore size on the two-dimentional carbon
molecule plane would increase amount of the transfer channel for
lithium (Li) ions. On the other hand, the controllable quantity and
even distribution of the hetero-atom would definitely increase the
storage sites for the Li more efficiently.
Rechargeable lithium-ion batteries (LIBs) have drawn much
attention for their advantages of high capacity, high working
voltage, and long cycling life.[1] Flexible electrodes, which can be
used in the LIBs, have received worldwide attentions because of
its remarkable application prospect in future portable devices.[2]
Carbon material including Carbon nanotube and Graphene, is
one of the most promising candidates for the flexible electrodes
due to their low cost, flexibility and easy synthesis, however, it is
also restricted by their fixed pore size in molecular structure,
which would be the steric hindrance for perpendicular diffusion of
Li ions.[3] Besides that, in order to further optimize the structure
and improve the performance of devices, the as-prepared carbon
material need to be annealed and doped with other hetero
element in high temperature, which would increase its
conductivity
and
crystallinity.[4]
Recently,
halogen
Herein, based on above consideration, we prepare a well-
defined two-dimensional carbon rich material named chlorine
substituted graphdiyne (Cl-GDY) through a bottom-to-up strategy,
which is a more efficient way to introduce hetero atoms into
carbon materials compared to the post-treating method. Cl-GDY
owns a graphdiyne-like two dimensional carbon framework,
comprising benzene rings (sp2 carbon) and butadiyne linkages
(sp carbon). The chlorine atoms are homogeneously distributed
in the two dimensional molecular plane, which would stabilize the
Li atoms intercalated in the Cl-GDY framework, and thus generate
more storage sites. Meanwhile, the substitution of chlorine on the
carbon framework enlarged the pore size in the two-dimensional
molecule plane, which may improve the Li ion diffusion situation
on the perpendicular direction. Finally, the Cl-GDY film on copper
foil was explored as an anode material in practical LIBs, which
achieved a highly improved reversible capacity of 1150 mA h g-1
at current density of 50 mA g−1 and a stable specific capacity
around 500 mA h g-1 for 500 cycles at the current density as higher
as 2 A g-1 in lithium ion half cells.
functionalization of carbon material has drawn much attention, as
it provides opportunities to optimize the conductivity, band gap
and morphology properties of carbon material due to the different
electronegativity and atom size of the halogen atoms.[5]
Compared to fluorine, chlorine has a larger atom size and a
moderate electronegativity.[6] The inclusion of chlorine in the
[a]
Dr. N. Wang, Mr. J. He, Dr. Z. Yang, Dr. F. Zhao, Mr. X. Li, Prof. C.
Huang, Dr. K. Wang, Prof. T. Jiu
Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese
Academy of Sciences. No. 189 Songling Road, 266101, Qingdao,
China.
E-mail: huangcs@qibebt.ac.cn
[b]
[c]
Mr. J. He, Mr. X. Li, Mr. Z. Tu
University of Chinese Academy of Sciences, No. 19A Yuquan Road,
100049, Beijing, China.
Mr. Z. Tu, Prof. Y. Yi, Prof. Y. Li
Beijing National Laboratory for Molecular Sciences (BNLMS), CAS
Key Laboratory of Organic Solids, Institute of Chemistry, Chinese
Academy of Sciences, Beijing 100190, China.
Briefly, 1,3,5-trichloro-2,4,6-triiodobenzene (compound 2)[12]
and 1,3,5-(trimethylsilyl)ethynyl-2,4,6-trichlorobenzene
Supporting information for this article is given via a link at the end of
the document.
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Scheme 1. The synthetic route of Cl-GDY
(compound 3)[13] were prepared follow typical procedures. Cl-
GDY was synthesized through the Glaser-Hay coupling reaction
of monomer, which was obtained from the compound 3 after
deprotection in the existence of tetrabutylammonium fluoride
(TBAF). The chemical structures of compound 3 and monomer
were confirmed through 1HNMR and 13CNMR (Figure S1-4 in
supporting information (SI)). As shown in Scheme 1, Cl-GDY is a
two-dimensional porous carbon-rich framework, with a repeated
hexagonal unit of connecting six 1,3,5-trichlorinebenzene rings
through butadiyne linkages. It should be noted that Cl-GDY is
endowed a unique π-conjugated carbon skeleton with expanded
pore size (the calculated diameter is about 1.6 nm as marked in
Scheme 1) on two-dimensional molecule plane, which comprises
chlorine atoms even distributing in the carbon framework in high
theoretical proportion (20 % in atomic number ratio, 42.5% in
weight ratio). Furthermore, the high contents and even distribution
of chlorine are expected to lead some interesting properties of Cl-
GDY.
As shown in Figure 1a, 1b and S5 (see SI), the carbon and
chlorine species were characterized by X-ray photoelectron
spectroscopy (XPS), respectively. In detail, the C 1s peaks of Cl-
GDY can be deconvoluted into five subpeaks of C-C (sp2) at 284.7
eV, C-C (sp) at 285.4 eV, C-Cl (sp2) at 286.6 eV, C-O at 287.5 eV
and C=O at 288.7 eV, respectively. Furthermore, the area ratio of
C-C (sp2), C-C (sp) and C-Cl (sp2) is close to 1:2:1, consistent with
the structure of Cl-GDY shown in Scheme 1. Besides that, in the
fitting peaks of carbon we also found the existence of C=O and
C-O groups, which may be due to the oxygenization of the
acetylene group in the margin of the two dimensional molecular
plane. Figure 1b shows high-resolution XPS scan for Cl 2p of the
Cl-GDY film, the prominent Cl 2p peaks at 200.6 eV (2p3/2) and
202.2 eV (2p1/2) are assigned to Cl-C bonds, obviously indicating
the covalent bond between Cl and carbon framework.[14] The
Raman spectra (Figure 1c) of the sample exhibit four main peaks.
A G-band at 1530 cm-1 suggests the samples possess abundant
aromatic rings, and a D-band at 1356 cm-1 is corresponding to
defects and edges.[15] The ratio of the peak intensity of D and G
band is 0.67, which indicates that the two-dimensional Cl-GDY
has relative high structure regularity. Furthermore, two peak at
2192 cm-1 and 1942 cm-1 can also be observed, which is ascribed
to acetylenic bond.[16] The structure of Cl-GDYs was further
investigated by Fourier transform infrared spectroscopy (FT-IR)
spectrum of as-grown Cl-GDYs on copper foil. The bands located
Figure 1. (a) XPS narrow scan for the element carbon in Cl-GDY. (b) XPS
narrow scan for the element chlorine in Cl-GDY. (c) Raman spectrum of Cl-GDY.
(d) FT-IR spectra of Cl-GDY film on copper foil. (e) Solid state 13CNMR of Cl-
GDY. (f) XRD patterns of Cl-GDY.
at 1500-1760 cm-1 are assigned to the skeletal vibrations of
aromatic ring. The band at 2200 cm-1 is the typical C≡C stretching
vibration. The stretching vibration and bending vibration of
aromatic C-Cl also can be observed at 900 cm-1. The peaks at
1000-1150 cm-1 may be contributed to the asymmetric stretching
mode of C-C bond. In contrast to the FT-IR spectrum of the 1,3,5-
trichlorine-2,4,6-triethynylbenzene monomer, it is clearly
observed the decreasing intensity of the acetylenic C-H vibration
over 3000 cm-1 which is corresponding to the cross-coupling
reaction of the monomer. Moreover, the decrease of the peak
intensity of C≡C stretching vibration and shift of skeletal vibrations
of aromatic ring to high wavenumber region also indicate the
increase of the conjugated carbon framework. All the above
characterization results verify the formation of the carbon rich
structure Cl-GDY. To further confirm the structure of Cl-GDY, the
solid state Nuclear Magnetic Resonance (NMR) experiment was
carried out. As shown in Figure1e, four kinds of carbons mainly
exist in the Cl-GDY framework. The peaks at 121.7 and 135.6
ppm correspond to the carbon atom in the benzene ring, which
are connected to the butadiyne and chlorine, respectively. The
peaks at 74.8 and 88.7 ppm can be ascribed to C(sp)-C(sp) and
C(sp)-C(sp2) sites. The XRD result of the as-synthesized samples
is shown in Figure 1f. The peaks at 23.6o for Cl-GDY can be
corresponded to the interlayer spacing of 3.76 Å, which is a
smaller interlayer distance compared to graphdiyne (4.05 Å).[11a]
Scanning electron microscopy (SEM) and element mapping as
well as transmission electron microscope (TEM) are used to
investigate the morphology of Cl-GDY films. The SEM images of
Cl-GDY on a copper substrate indicate that this film is uniform and
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Figure 2. (a, b) The morphology of the as-prepared Cl-GDY film. (c) SEM images of Cl-GDY film. (d, e) The cross-section SEM image of Cl-GDY film Element
mapping of the Cl-GDY film. (f) The photograph of free-standing Cl-GDY film exfoliated from the copper foil. (g) TEM image of Cl-GDY film. (h, i) HRTEM and
corresponding SAED images of Cl-GDY on ultra-thin carbon film. (j) The photograph flexible Cl-GDY film.
porous (Figure 2a and 2b). Moreover, the morphology of thin film
at the side close to the copper substrate is more compact than
that at the other side away from the copper (Figure 2c), and some
substrate were shown in Figure 3b, which contain irreversible
capacity in the first cycle. This is because extensive solid
electrolyte interface (SEI) layers were formed during the first
Cl-GDY fibers are observed on the surface of the as-prepared film, discharge pcrocess. Figure 3c-e, Fiugre S7a and S7b (see SI)
which might be due to the subtle alternation of coupling reaction show the long cycle performance of the as-prepared electrodes
environment at different stages of the Cl-GDY film growth process. under different current densities. The Cl-GDY films exhibit
The thickness of the sample is approximately 2.77 μm with
weighed mass density of 0.58 g cm-3. Element mappings reveal
the uniform distribution of the carbon and chlorine atoms in Cl-
GDY (Figure 2d and 2e). The as-prepared Cl-GDY film in our
condition is black and untransparent with length of 1 cm and width
of 1 cm (Figure 2f). High resolution TEM (HRTEM) and
corresponding selected area electron diffraction (SAED) of TA-
GDY film are showed in Figure 2g and h. The layer-to-layer
distance is 0.376 nm according to the HRTEM image (Figure 2i),
which is consistent with that of the XRD spectrum. It is notable
that the Cl-GDY film is flexible, which shows an excellent
mechanical strength (Figure 2j). Moreover, the conductivity of Cl-
GDY film is measured to be 1.972×10-3 S m-1 (see Figure S6 in
SI), which indicates a more excellent transport property than that
of graphdiyne (2.516×10-4 S m-1),[11a] due to the inclusion of
chlorine in the two-dimensional molecular plane.[7,8]
The electrochemical performances with Cl-GDY-based
electrodes were evaluated through a standard CR2032-type coin
cells with lithium metal foils as counter electrodes. Figure 3 shows
the electrochemical performances of the Cl-GDY-based
electrodes used in LIBs in the potential range of 0.005-3 V versus
Li+/Li. Figure 3a shows the rate performance Cl-GDY from 0.05 to
5 A g-1. When the current density increased to 5 A g-1, the
inreversible capacity of our sample can even be kept at 300 mAh
g-1. In addition, the capacity of the sample can be fully recovered
after cycled at various current density. The charge-discharge
profiles of the initial three cycles for Cl-GDY films on copper
superior capacity retention ability at different current densities.
The reversible capacity can reach 1150 and 500 mAh g-1 after 100
cycles at the current density of 0.05 and 2 A g-1 for Cl-GDY,
respectively. The coulombic efficiency of those sample was
approximately 97% in average at the current density of 0.05 A g-1
and approximately 95% in average at the current density of 2 A g-
1
.
As shown in Table S1, Cl-GDY shows improved
electrochemical performance in LIBs compared to that of GDY,
which is ascribed to inclusion of the chlorine in the Cl-GDY
framework. The cyclic voltammogram (CV) curves (Figure S8 in
SI) were summarized from the initial three cycles, with scan rate
as 0.1 mV/s. During the first cathodic scan, an irreversible band
appears in the range of 1.0 to 1.5 V, which is attributed to the
electrochemical decomposition of electrolyte for the formation of
SEI film on the electrode surface. It is disappeared from the 2nd
cycle, suggesting the formation of stable SEI layer on the Cl-GDY
film (Figure S9 in SI). The much higher formation voltage of SEI
film could be due to the containing of chlorine heteroatoms on the
surface of electrode,[1d,9] which might have interaction with some
components in the electrolyte solution and accelerate their
deposition.[4b] Figure S10 (see SI) shows Nyquist plots of Cl-GDY
electrodes before and after 3 cycles at a current density of 500
mA g-1, which are both composed of a depressed semicircle arc
in the high-to-medium frequency region and a linear tail in the low
frequency region. For the fresh electrode, the semicircle is ascribe
to the charge transfer process because of the absence of SEI film
before cycling, however, the semicircle in the Nyquist plot after
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Figure 3. The electrochemical performance of Cl-GDY flexible electrodes in Li metal half-cell format. (a) The rate performance of the electrode for LIBs. (b) The
charge-discharge profiles of a Cl-GDY electrode at a current density of 50 mA/g. The cycle performance of flexible electrode at 50 mA/g (c), 200 mA/g (d), 2 A/g
(e). (f) The geometries and formation energies (Ebinding) of four optimized Li+C28Cl6 (A1-A4) complex and one optimized 2Li+C28Cl6 (B1). (g, h) The possible Li
storage sites in Cl-GDY and the function of chlorine (gray circles: C; green circles: Cl; orange circles: Li).
three cycles is attributed to combination resistance of SEI film and
charge transfer process (Table S2), which possesses much lower
electrolyte resistance (Re) and charge-transfer resistance (Rct)
compared to those of the fresh electrodes, indicating more
unhindered electron transfer and diffusion of lithium ions in the
electrode during cycling.[1d]
system.[17] This can be owned to the synergistic stabilization effect
of chlorine atom on the ortho-position of butadiyne group (see
configuration A1 and A2). This phenomenon can be understood
from the appropriate electronegativity and atom size of chlorine,
which make it can stabilize the Li atom intercalated on the
butadiyne group through coordination effect. Moreover, while two
Li atoms were put on the butadiyne group, a stable and effective
configuration (B1) with a binding energy of -1.39 eV was obtained,
which further confirmed the stabilization effect of chlorine for the
Li atoms on the butadiyne groups. It is worth emphasizing that
chlorine are even distributed in the Cl-GDY molecule plane in our
designed molecule plane, so the ortho-stabilization effect of
chlorine for the Li atoms is effective for all the butadiyne groups
in the molecule plane. This can be further confirmed by the XPS
spectra of SEI film (Figure S11 in SI). While Li cations intercalated
into the Cl-GDY framework, the peak of chlorine (Cl-C) shifts to
the lower energy, which proves the interaction between the
chlorine and the Li in experiment. As calculated and shown in
Figure S12 (see SI), the diffusion barrier of Li on Cl-GDY is
significantly reduced compared to that of graphdiyne, which is
also beneficial to improve the electrochemical performance of Cl-
GDY based electrode in LIBs.
To understand the fuction of chlorine for the Li-ions intercalation
in the anode containing Cl-GDY, density functionalm theory (DFT)
calculation was applied for our system. Firstly, we just focused on
the Li storage situation of one selected repeating unit in the single
Cl-GDY molecule plane. As shown in Figure 3f, the stabilities of
(Li)n-C28Cl6 complexes were examined by their binding energies.
When only one Li was added, four possible Li-C28Cl6
configurations were obtained. The Li may be located either on the
different positions of butadiyne groups (A1-A3) or above the
benzene ring (A4), which is substituted with three chlorine and
three acetylene groups. Interestingly, the configurations A1-A3
show binding energies in the range of -1.40 eV to -1.49 eV, which
are much larger than that of configuration A4 (-1.09 eV). The
result indicates that the complexes with Li on the butadiyne
groups are more stable than that on the benzene ring in our Cl-
GDY system, which is opposite comparing to that of graphdiyne
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Based on the above discussion, we try to find the optimized
configuration for the maximum Li storage in Cl-GDY based
electrode. It can be seen from configuration B in Figure 3f, while
more Li are intercalated, the distance between the Li and chlorine
atoms are decreased, which maybe induce the tortuosity of the
configuration. Considering the rigidity of the Cl-GDY framework,
a symmetrical configuration in Figure 3g and 3h was selected,
which could avoid the tortuosity of the molecule framework and
guarantee the maximum Li atoms number intercalated in the
system. It should be noted that there have been six Li atoms
around the benzene ring in this configuration, so no more Li atoms
are put above the benzene ring to avoid the overcrowding of Li
cations. Finally, we predict that the ratio of carbon and Li in a
repetitive unit is 12:12. The calculated capacity value is 1284
mAhg−1, which is in good agreement with our experiment result.
However, this value is still the lower limit of theoretical capacity,
for many pores and defects existing in the multiple layers of Cl-
GDY molecular plane can provide more storage sites for Li atoms.
(JQ201610) and the National Basic Research 973 Program of
China (2012CB932900).
Keywords: Graphdiyne • Chlorine • Two-dimension • Carbon
material • Energy storage
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In summary, we prepared chlorine substitutional graphdiyne
(Cl-GDY) film, which had highly conjugated structure and uniform
large pores on the two-dimensional molecule plane with a
repeated unit of connecting six 1,3,5-trichlorinebenzene rings
through six butadiyne linkages. The unique two-dimensional
structure endowed Cl-GDY more transfer tunnels for the Li ions
on the perpendicular direction of the molecule plane. meanwhile,
the amount of Li storage sites was increased. As a result, LIBs
with Cl-GDY as electrode showed excellent rate performances
and extraordinary cycling stability. A remarkable charge capacity
of 1150 mA h g−1 at current density of 50 mA g−1 and a stable
specific capacity around 500 mA h g-1 for 200 cycles at the current
density as higher as 2 A g-1 were obtained. Our results indicate
that the inclusion of chlorine atoms evenly and quantificationally
in the carbon rich materials with uniform large pores on molecular
plane is an efficient strategy to improve their electrochemical
performance. The new carbon-rich flexible Cl-GDY film has
shown good potential for application in the field of energy storage.
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This study was supported by the “Hundred Talents Program” of
the Chinese Academy of Sciences, the Strategic Priority
Research Program of the Chinese Academy of Sciences (Grant
No. XDB12020200), the Natural Science Foundation of
[17]
Shandong Province (China) for Distinguished Young Scholars
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Entry for the Table of Contents
COMMUNICATION
Chlorine substitutional graphdiyne
(Cl-GDY) is prepared through bottom-
to-up chemical strategy. Cl-GDY is
Ning Wang, Jianjiang He, Zeyi Tu, Ze
Yang, Fuhua Zhao, Xiaodong Li,
Changshui
Huang*,
Kun
Wang,
endowed
a
unique structure with
Tonggang Jiu, Yuanping Yi, and Yuliang
Li
expanded pore size and even-
distribution of chlororine in the π-
conjugated carbon skeleton, which will
synergistically stabilize the lithium
atom intercalated in the Cl-GDY
framework. Benefiting from the above
unique structure, Cl-GDY shows
Page No. – Page No.
Synthesis of Chlorine-substituted
Graphdiyne and Its Application for
Lithium-ion Storage
remarkable
electrochemical
performance in lithium ion half cells.
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