Hollow and microporous triphenylamine networks post-modified with TCNE for enhanced organocathode performance

Article abstract of DOI:10.1039/c7cc03343e

Hollow microporous triphenylamine networks (H-MTPN) were post-modified with tetracyanoethylene (TCNE) to generate tetracyanobutadiene moieties in H-MTPN-TCNE. The H-MTPN-TCNE showed the improved electrochemical performance of cathode materials for lithium ion batteries, compared to the original H-MTPN.

Full text of DOI:10.1039/c7cc03343e

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Hollow and microporous triphenylamine networks post-modified
with TCNE for enhanced organocathode performance
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
b
b
c
Jaewon Choi,‡ Eui Soon Kim,‡ Ju Hong Ko, Sang Moon Lee, Hae Jin Kim, Yoon-Joo Ko, and
a
Seung Uk Son*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Hollow microporous triphenylamine networks (H-MTPN) were the redox active MONs with hollow structures can be
post-modified with tetracyanoethylene (TCNE) to generate promising as electrode materials.
tetracyanobutadiene moieties in H-MTPN-TCNE. The H-MTPN-
TCNE showed the improved electrochemical performance of reaction
Triphenylamines showing a reversible one-electron redox
7
,12
13
and tetracyanoalkenes showing a reversible two-
cathode materials for lithium ion batteries, compared to the electron redox reaction have been used as redox active moieties
original H-MTPN.
in organic cathode materials. (Fig. 1a) In this work, we report
the synthesis of hollow MON materials containing
triphenylamine moieties (H-MTPN), the post-modification of
H-MTPN with tetracyanoethylene (TCNE) to form H-MTPN-
TCNE, and the enhanced electrochemical performance of H-
MTPN-TCNE as cathode materials in lithium ion batteries.
Fig. 1b shows a synthetic scheme for H-MTPN-TCNE.
As energy storage becomes an important issue, extensive
studies are underway on new energy storage materials. Among
various electrode materials for lithium ion batteries, organic
cathode materials have attracted significant attention of
scientists due to their sustainability, environmentally benign
1
2
nature, and promising capacities. In this regard, various
(a)
organic redox molecules have been applied as cathode
NC
NC
3
materials. However, the molecules can be leached into
e-
CN
+2e-
CN
+
electrolyte solution during charge/discharge processes, resulting
in the decrease of capacities. Thus, the efficient fixation of
organic redox moieties is important to overcome the leaching
problems. In addition, further exploration is required for the
enhancement of storage capacities.
N
-e
-
N
2e-
-
NC
NC
CN
CN
(
b)
I
I
4
N
+I
N
AcOH
Recently, microporous organic networks (MONs) have been
ZIF-8
@MTPN
ZIF-8
5
prepared by coupling of various organic building blocks.
Sonogashira
coupling
Conventional MONs are insoluble in solvents and highly
porous in nature. The redox active moieties can be incorporated
into MON materials through a predesigned building block
Hollow MTPN
H-MTPN)
(
6
approach. Moreover, due to the existence of micropores, the
N
N
NC
NC
CN
CN
redox active moieties in inner MON can be utilized in
electrochemical events. Thus, MON materials are promising for
the engineering of organic electrode materials for lithium ion
batteries. Recently, organic cathode materials based on MON
Color
change
Microporous
triphenylamine network
MTPN)
TCNE
Post synthetic
modification
(
NC
7
chemistry have been reported, in which most studies used
CN
N
N
powdery materials with irregular morphologies.
NC
CN
Our research group has reported the shape engineering
8
methods of MON materials. Especially, hollow MON
TCNE adductof H-MTPN
H-MTPN-TCNE)
8
(
materials have been prepared by template methods. The
hollow MON materials with thin shells have an advantage in Fig. 1 (a) Redox behaviors of triphenylamine and tetracyano-
1
0
butadiene derivatives. (b) Synthetic scheme for hollow and
microporous triphenylamine network (H-MTPN) and its TCNE
adduct (H-MTPN-TCNE).
facile post-modification. Moreover, hollow MON materials
provide the short diffusion pathways of guests including
electrolytes in the utilization of inner functional species. Thus,
1
1
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J. Name., 2013, 00, 1-3 | 1
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For the preparation of H-MTPN, Zn-based zeolitic
imidazolate framework (ZIF-8) was used as a template. Using the coating of ZIF-8 with MTPN. H-MTPN and H-MTPN-
tri(4-ethynylphenyl)amine and tri(4-iodophenyl)amine as TCNE showed amorphous characteristics, matching well with
Journal Name
As shown in Fig. 2f, the structure of ZIF-8 was VrieetwaAinrtiecdle Oanfltiener
1
4
DOI: 10.1039/C7CC03343E
1
5
building blocks, microporous organic networks bearing the property of MONs in the literature. The analysis of N
triphenylamines were formed on the surface of ZIF-8 particles adsorption-desorption isotherm curves of H-MTPN showed the
2
2
3
by the Sonogashira coupling to form ZIF-8@MTPN. The ZIF-8 surface area of 767 m /g and microporosity (Vmic: 0.18 cm /g).
in ZIF-8@MTPN was easily removed by the treatment with (Fig. 2g) The post-modification of H-MTPN with TCNE
1
3
acetic acid to form orange colored H-MTPN. The heating of resulted in the decrease of the surface area and micropore
2
3
H-MTPN with TCNE resulted in H-MTPN-TCNE materials. volume to 589 m /g and 0.13 cm /g, matching well with the
The materials were investigated by scanning (SEM) and common observations in the post-modified MON materials.
1
6
transmission electron microscopy (TEM). (Figs. 2a-e and S1 in
the ESI)
One of the interesting observations in the post-modification
of H-MTPN with TCNE was a vivid color change from orange
(

abs: 391 nm) to very dark (The
corresponds to post-modified and intact materials, respectively).
Fig. 3b) To confirm the post-modification, we conducted
model studies. As shown in Fig. 3a, first model compound
4,4’-(ethyne-1,2-diyl)bis(N,N-diphenylaniline), TP) was
abs of 500 and 391 nm
(
a)
d)
(b)
(c)
(
(
prepared by the Sonogashira coupling of 4-ethynylphenyl-N,N-
diphenylamine with 4-iodophenyl-N,N-diphenylamine. The
treatment of TP with TCNE resulted in second model
compound (TP-TCNE) with the vivid color change from yellow
200 nm
200 nm
200 nm
(
(e)
(abs: 374 nm) to very dark (abs: 489 nm). (Fig. 3a) The color
change by reaction with TCNE originates from a photo-induced
intramolecular charge transfer between electron rich
triphenylamine to electron deficient cyano groups, supporting
the reaction of an internal alkyne with TCNE. The chemical
structures of model compounds were fully characterized. (Fig.
S2 and the ESI) The reactions of internal alkynes with TCNE
1
7
and their color changes have been reported in the literature.
200 nm
200 nm
NC
CN
NC
CN
(
f)
(g)
NC
CN
N
(a)
N
N
Heat
,2-Cl2CH2CH2
N
NC
1
CN
TP
ZIF-8
TP-TCNE
(
b)
TP
ZIF-8@MTPN
H-MTPN
H-MTPN
H-MTPN
-TCNE
TP-TCNE
H-MTPN-TCNE
H-MTPN
H-MTPN-TCNE
(
c)
Fig. 2 SEM and TEM images of (a) ZIF-8 nanoparticles, (b) ZIF-
@MTPN, (c) H-MTPN, and (d-e) H-MTPN-TCNE. (f) PXRD patterns
of ZIF-8, ZIF-8@MTPN, H-MTPN, and H-MTPN-TCNE. (g) N sorption
isotherm curves at 77K and pore size distribution diagrams (based
on the DFT method) of H-MTPN and H-MTPN-TCNE.
TP-TCNE
H-MTPN
TP
H-MTPN
H-MTPN
8
2
H-MTPN
-
TCNE
-
TCNE
As shown in Figs 2a-b, the ZIF-8 nanoparticles with average
C
C
C
N
size of 128
± 13 nm were coated homogeneously with MTPN
(
15 1 nm thickness) through the Sonogashira coupling of
±
building blocks. The hollow structure of H-MTPN was
confirmed through the TEM analysis. (Fig. 2c) The hollow
morphology was retained after the post-modification of H- absorption spectra and photographs of TP (pale yellow), TP-TCNE
Fig. 3 (a) Model reaction of H-MTPN with TCNE to form H-MTPN-
TCNE: The reaction of TP with TCNE to form TP-TCNE. (b) UV-vis
(
dark), H-MTPN (orange), and H-MTPN-TCNE (dark). (c) IR spectra of
MTPN with TCNE. The average size and shell thickness of H-
MTPN-TCNE were measured as 157 14 nm and 16 1 nm,
respectively. (Figs. 2d-e and S1 in the ESI)
TP, TP-TCNE, H-MTPN, and H-MTPN-TCNE.
±
±
2
| J. Name., 2012, 00, 1-3
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Infrared (IR) absorption spectroscopy of H-MTPN-TCNE the additional tetracyanobutadiene moieties. ConViseiwdAerrtiicnlegOntlhinee
-
1
DOI: 10.1039/C7CC03343E
showed the appearance of a new peak at 2221 cm , which is amount of triphenylamine (3.1 and 2.6 mmol/g for H-MTPN
1
8
assigned to CN stretching and matches with the trend in the and H-MTPN-TCNE, respectively) and tetracyanobutadiene
IR spectrum of TP-TCNE. (Fig. 3c) The chemical structures of (1.3 mmol/g for H-MTPN-TCNE) based on elemental analysis,
H-MTPN and H-MTPN-TCNE were further investigated by theoretical capacities were calculated as 82 mAh/g and 139
solid phase C nuclear magnetic resonance spectroscopy mAh/g for H-MTPN and H-MTPN-TCNE. The observed
NMR). (Fig. 4) The C peaks of internal alkyne and aromatic discharge capacities of H-MTPN (72 mAh/g after 100 cycles)
1
3
22
1
3
(
carbons adjacent to the nitrogen of H-MTPN were observed at and H-MTPN-TCNE (123 mAh/g after 100 cycles) matched
8
1
9 and 146 ppm, respectively, matching with those at 89 and well with the expected values. It is noteworthy that cathode
47 ppm of the model compound, TP. After post-modification, MONs containing triphenylamines have shown the discharge
1
3
7
the C NMR of H-MTPN-TCNE changed significantly with a capacities in a range of 50~ 100 mAh/g in the literature. At the
new peak at 165 ppm, resulting from the chemical reaction of current densities of 0.1, 0.2, 0.5, 1, and 2 A/g, H-MTPN-TCNE
1
9
13
internal alkynes with TCNE. The trend of C NMR of H- showed the discharge capacities of 120, 107, 92, 80, and 72
MTPN-TCNE matched with those of TP-TCNE. The elemental mAh/g, respectively. (Fig. 5b) The coulombic efficiency of H-
analysis showed the increase of N contents from 4.3 (3.1 mmol MTPN increased from 76 to 97 % during the first 5 cycles and
N/g) to 10.9w% (7.8 mmol N/g) through the post-modification maintained values above 97% in next cycles. In the case of H-
of H-MTPN with TCNE, indicating that the ~34% of internal MTPN, coulombic efficiency increased from 74 to 94 during
2
0
alkynes were modified with TCNE (1.3 mmol TCNE/g).
the first 70 cycles and maintained values above 97%. (Fig. 5c)
C2-3
(
a)
C1
C4
C5
H-MTPN
2
3
H-MTPN-TCNE
H-MTPN
1
4 5
N
N
Model TMS
TP
C2-4
C7
C1
C5
H-MTPN
-TCNE
(
b)
(c)
C6
NC
6
4
5
7
CN
2
3
H-MTPN-TCNE
H-MTPN
1
H-MTPN
-TCNE
N
CDCl3
N
NC
50
50
mA/g
CN
mA/g 100
mA/g 200
mA/g 500
mA/g
Model
TP-TCNE
1
A/g
2
A/g
H-MTPN
1
3
Fig. 4 Solid and liquid phase C NMR spectra of TP, TP-TCNE, H-
MTPN, and H-MTPN-TCNE.
(d)
(e)
Next, we studied the electrochemical performance of H-
MTPN and H-MTPN-TCNE for lithium ion batteries. Fig. 5
H-MTPN
-TCNE
H-MTPN
-TCNE
2
1
summarizes the results. Coin cells were fabricated using H-
MTPN and H-MTPN-TCNE as cathode materials and lithium
metal as anode materials. The charge-discharge processes were
H-MTPN
H-MTPN
+
cycled in a range of 1.5 ~ 4.2 V (vs Li/Li ). As shown in Fig. 5a,
the discharge capacities of H-MTPN-TCNE (current density:
5
0 mA/g) decreased gradually from 159 mAh/g to 133 mAh/g
during the first 20 cycles. The discharge capacities maintained
23 mAh/g (92% of that of 20 cycle) after 100 cycles. The
Fig. 5 (a) Cycle tests with a 50 mA/g current density and a 0.22
2
21
mg/cm loading , (b) rate performance, (c) coulombic efficiency, (d)
charge-discharge profiles, and (e) impedance of H-MTPN and H-
MTPN-TCNE.
1
extended cycle tests (current density: 100 mA/g) showed that
the H-MTPN-TCNE maintained 91% (106 mAh/g) of the
discharge capacity (117 mAh/g) of the first cycle after 500
Compared to those of H-MTPN, the charge-discharge
cycles. (Fig. S3 in the ESI) In the case of H-MTPN, discharge profiles of H-MTPN-TCNE showed additional redox activities
+
capacities decreased from 103 mAh/g to 80 mAh/g during the in a range of 1.5~3.5 V (vs Li/Li ), which is attributable to the
1
3
first 20 cycles and were maintained at 72 mAh/g (90% of that redox reaction of tetracyanobutadiene moieties. (Figs. 5d and
of 20 cycle) after 100 cycles. The enhanced storage capacity of S4-7 in the ESI) The Nyquist plots through impedance
H-MTPN-TCNE, compared to that of H-MTPN, resulted from measurement of H-MTPN-TCNE and H-MTPN showed the
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Journal Name
Zhang, Z. Chang, J. Han, X. –P. Gao and X. –H.VBieuw,ARrtiSclCe OAndlinve.
014, , 7506-7510; (d) K. Sakaushi, E. Hosono, G. Nickerl, H.
Zhou, S. Kaskel and J. Eckert, J. Power Sources 2014, 245, 553-
56; (e) S. Zhang, W. Huang, P. Hu, C. Huang, C. Shang, C.
Zhang, R. Yang and G. Cui, J. Mater. Chem. A 2015, , 1896-
charge transfer resistances of 93 and 165 Ω, respectively. (Fig.
2
4
DOI: 10.1039/C7CC03343E
5
e) The enhanced charge transfer ability of H-MTPN-TCNE,
compared with H-MTPN can be attributed to the incorporation
of additional redox active moieties to H-MTPN. The
microscopic analysis on the H-MTPN-TCNE recovered after
cycles showed the complete maintenance of original hollow
morphologies, indicating the robustness of MON materials.
5
3
1901; (f) C. Zhang, X. Yang, W. Ren, Y. Wang, F. Su and J. –X.
Jiang, J. Power Sources 2016, 317, 49-56; (g) W. Zhou, H. Cao
and J. B. Goodenough, Adv. Energy Mater. 2016,
501802l.
6, 1501802-
1
(
Refer to SEM and TEM images in Figs. S8-9 in the ESI)
In conclusion, this work shows that the hollow and redox
8
(a) J. Chun, S. Kang, N. Park, E. J. Park, X. Jin, K. –D. Kim, H.
O. Seo, S. M. Lee, H. J. Kim, W. H. Kwon, Y. –K. Park, J. M.
active MON materials can be applied as electrode materials for
lithium ion batteries. Moreover, the post-modification of MONs
with redox active species can further enhance the
electrochemical performance. The post-synthetic strategy in
this work can be applied to various MON materials which
have been prepared by the Sonogashira coupling. Thus, we
believe that electrochemical performance can be further
improved through the screening of building blocks.
Kim, Y. D. Kim and S. U. Son, J. Am. Chem. Soc. 2014, 136
786-6789; (b) J. Chun, J. H. Park, J. Kim, S. M. Lee, H. J. Kim
and S. U. Son, Chem. Mater. 2012, 24, 3458-3463.
N. Kang, J. H. Park, M. Jin, N. Park, S. M. Lee, H. J. Kim, J. M.
Kim and S. U. Son, J. Am. Chem. Soc. 2013, 135, 19115-19118.
0 K. Cho, J. Yoo, H. –W. Noh, S. M. Lee, H. J. Kim, Y. –J. Ko, H.
,
6
9
1
1
1
1
5
–Y. Jang and S. U. Son, J. Mater. Chem. A 2017,
1 X. Wang, J. Feng, Y. Bai, Q. Zhang and Y. Yin, Chem. Rev.
016, 116, 10983-11060.
5, 8922-8926.
2
2 (a) J. K. Peng, Y. L. Cao, X. P. Ai and H. X. Yang, J. Power
Sources 2008, 177, 199-204; (b) C. Su, Y. Ye, L. Xu and C.
Zhang, J. Mater. Chem. 2012, 22, 22658-22662; (c) C. Su, F.
Acknowledgements
Yang, L. Ji, L. Xu and C. Zhang, J. Mater. Chem. A 2014,
0083-20088; (d) J. Xiang, R. Burges, B. H upler, A. Wild, U. S.
Schubert, C. –L. Ho and W. –Y. Wong, Polymer 2015, 68, 328-
34.
KBSI (R&D Convergence Program) of National Research Council 13 Y. Hanyu and I. Honma, Sci. Rep. 2012,
2,
This work was supported by Basic Science Research Program
2
ä
(
2016R1E1A1A01941074) through the NRF funded by the Ministry
of Science, ICT and Future Planning and the grants CAP-15-02-
3
2
, 453-458.
of Science & Technology (NST) of Korea.
14 (a) K. S. Park, Z. Ni, A. P. Cȏté, J. Y. Choi, R. Huang, F. J.
Uribe-Romo, H. K. Chae, M. O’Keeffe, O. M. Yaghi, Proc. Natl.
Acad. Sci. U. S. A. 2006, 103, 10186-10191; (b) N. L. Torad, M.
Hu, Y. Kamachi, K. Takai, M. Imura, M. Naito and Y. Yamauchi,
Chem. Commun. 2013, 49, 2521-2523; (c) L. He, L. Li, S. Zhang,
S. Xing, T. Wang, G. Li, X. Wu, Z. Su and C. Wang,
CrystEngComm, 2014, 16, 6534-6537.
Notes and references
a.
Department of Chemistry, Sungkyunkwan University, Suwon 16419,
Korea E-mail: sson@skku.edu
Korea Basic Science Institute, Daejeon 34133, Korea
Laboratory of Nuclear Magnetic Resonance, NCIRF, Seoul National
b.
c.
15 J. –X. Jiang, F. Su, A. Trewin, C. D. Wood, N. L. Campbell, H.
Niu, C. Dickinson, A. Y. Ganin, M. J. Rosseinsky, Y. Z.
University, Seoul 08826, Korea
‡
These authors contributed equally to this work.
Khimyak and A. I. Cooper, Angew. Chem., Int. Ed. 2007, 46,
†
Electronic Supplementary Information (ESI) available: Synthetic
8574-8578.
procedure, characterization of new compounds, cyclovoltammograms, 16 (a) W. Lu, J. P. Sculley, D. Yuan, R. Krishna, Z. Wei and H. –C.
and SEM images of H-MTPN-TCNE recovered after cycles. See
DOI: 10.1039/x0xx00000x
Xhou, Angew. Chem. Int. Ed. 2012, 51, 7480-7484; (b) H. A.
Patel and C. T. Yavuz, Chem. Commun. 2012, 48, 9989-9991; (c)
B, Kiskan and J. Weber, ACS Macro Lett. 2012,
Thiel, R. Zehbe, J. Roeser, P. Strauch, S. Enthaler and A.
Thomas, Polym. Chem. 2013, , 1848-1856.
, 2280-2301; (c) T. B. Schon, B. T. McAllister, P. –F. Li 17 (a) T. Michinobu, C. Seo, K. Noguchi and T. Mori, Polym. Chem.
1, 37-40; (d) K.
1
Reviews: (a) Y. Liang, Z. Tao and J. Chen, Adv. Energy Mater.
2
2
012,
013,
2
6
, 742-769; (b) Z. Song and H. Zhou, Energy Environ. Sci.
4
and D. S. Seferos, Chem. Soc. Rev. 2016, 45, 6345-6404.
Review: Y. Zhang, J. Wang and S. N. Riduan, J. Mater. Chem. A.
2012,
Gisselbrecht, W. B. Schweizer and F. Diederich, Eur. I. Org.
Chem. 2013, , 869-879.
(a) M. Armand and J. –M. Tarascon, Nature 2008, 451, 652-657; 18 The CN vibration peaks of tetracyanobutadiene derivatives
3, 1427-1435; (b) A. R. Lacy, A. Vogt, C. Boudon, J. –P.
2
3
2
016,
4
, 14902-14914.
5
-
1
(
b) M. Armand, S. Grugeon, H. Vezin, S. Laruelle, P. Ribi
Poizot and J. –M. Tarascon, Nat. Mater. 2009, , 120-125.
S. Muench, A. Wild, C. Friebe, B. H upler, T. Janoschka and U.
è
re, P.
appeared in a range of 2220~2222 cm in the literature. T. Shoji,
S. Ito, K. Toyota, M. Yasunami and N. Morita, Chem. Eur. J.
2008, 14, 8398-8408.
8
4
5
ä
1
3
S. Schubert, Chem. Rev. 2016, 116, 9438-9484.
Reviews: (a) Y. Xu, S. Jin, H. Xu, A. Nagai and D. Jiang, Chem.
Soc. Rev. 2013, 42, 8012-8031; (b) R. Dawson, A. I. Cooper and
19 The C peaks of butadiene moieties in tetracyanobutadiene
derivatives appeared at 88~89 and 164~167 ppm in the literature.
Refer to ref. 14b.
D. J. Adams, Prog. Poly. Sci. 2012, 37, 530-563; (c) F. Vilela, K. 20 Considering the 4.3w% N in H-MTPN and 43.7w% N in TCNE,
Zhang and M. Antonietti, Energy Environ. Sci. 2012,
5
, 7819-
832; (d) A. Thomas, Angew. Chem. Int. Ed. 2010, 49, 8328-
344; (e) N. B. McKeown and P. M. Budd, Chem. Soc. Rev. 2006,
, 675-683.
the 10.9w% in H-MTPN-TCNE was analyzed to 3.6w% N from
triphenylamine and 7.3w% N from TCNE. Thus, the amounts of
triphenylamine, alkynes, and the added TCNE were calculated to
2.6, 3.8 and 1.3 mmol/g, respectively.
7
8
3
5
6
7
N. Kang, J. H. Park, J. Choi, J. Jin, J. Chun, I. G. Jung, J. Jeong, J. 21 T. Nokami, T. Matsuo, Y. Inatomi, N. Hojo, T. Tsukagoshi, H.
–
G. Park, S. M. Lee, H. J. Kim and S. U. Son, Angew. Chem. Int.
Yoshizawa, A. Shimizu, H. Kuramoto, K. Komae, H. Tsuyama
Ed. 2012, 51, 6626-6630.
and J. –I. Yoshida, J. Am. Chem. Soc. 2012, 134, 19694-19700.
(a) K. Sakaushi, E. Hosono, G. Nickerl, T. Gemming, H. Zhou, S. 22 The theoretical capacities are based on one-electron redox
Kaskel and J. Eckert, Nat. Commun. 2013,
Xu, X. Chen, Z. Tang, D. Wu, R. Fu and D. Jiang, Chem.
Commun. 2014, 50, 4788-4790; (c) D. Tian, H. –Z. Zhang, D. –S.
4
, 1485-1491; (b) F.
process of triphenylamine moieties and two-electron redox
process of tetracyanobutadiene moieties.
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| J. Name., 2012, 00, 1-3
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