A Bipolar and Self-Polymerized Phthalocyanine Complex for Fast and Tunable Energy Storage in Dual-Ion Batteries

Article abstract of DOI:10.1002/anie.201904242

Bipolar redox organics have attracted interest as electrode materials for energy storage owing to their flexibility, sustainability and environmental friendliness. However, an understanding of their application in all-organic batteries, let alone dual-ion batteries (DIBs), is in its infancy. Herein, we propose a strategy to screen a variety of phthalocyanine-based bipolar organics. The self-polymerizable bipolar Cu tetraaminephthalocyanine (CuTAPc) shows multifunctional applications in various energy storage systems, including lithium-based DIBs using CuTAPc as the cathode material, graphite-based DIBs using CuTAPc as the anode material and symmetric DIBs using CuTAPc as both the cathode and anode materials. Notably, in lithium-based DIBs, the use of CuTAPc as the cathode material results in a high discharge capacity of 236 mAh g^?1 at 50 mA g^?1 and a high reversible capacity of 74.3 mAh g^?1 after 4000 cycles at 4 A g^?1. Most importantly, a high energy density of 239 Wh kg^?1 and power density of 11.5 kW kg^?1 can be obtained in all-organic symmetric DIBs.

Full text of DOI:10.1002/anie.201904242

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Accepted Article
Title: A bipolar and self-polymerized phthalocyanine complex for fast
and tunable energy storage
Authors: Shuyan Song, Hengguo Wang, Lanlan Wu, Yu Liu, Haidong
Wang, Zhenjun Si, Qiang Li, Qiong Wu, Qi Shao, Yinghui
Wang, and Hongjie Zhang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201904242
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COMMUNICATION
A bipolar and self-polymerized phthalocyanine complex for fast
and tunable energy storage
Heng-guo Wang,[a,b] Haidong Wang, Zhenjun Si, Qiang Li, Qiong Wu, Qi Shao, Lanlan Wu,
[b]
[b]
[b]
[b]
[b]
[a]
[
a]
[a]
[a]
[a]
Yu Liu, Yinghui Wang, Shuyan Song* and Hongjie Zhang
Abstract: Bipolar redox organics have attracted immense scientific
interest as electrode materials for energy storage due to their
flexibility, sustainability and environmental friendliness. However, an
understanding of their application in all-organic batteries, let alone
dual-ion batteries (DIBs), is in its infancy and demands prompt
attention. Herein, we propose a molecular-level design strategy to
screen a variety of phthalocyanine-based bipolar organics. Based on
the bipolar and self-polymerized features, the resulting Cu
have attracted widespread interest for EESs.[7] For n-type
organics, the neutral state first accepts electrons to form a
+
+
+
negatively charged state, and then cations (Li , Na , K or even
+
H ) can be used to neutralize the negative charge. Whereas for
p-type organics, electrons can first be extracted to form a
positively charged state, then anions (PF -
, ClO -
, BF
-
or TFSI-)
6
4
4
can be used to neutralize the positively charged state. By
contrast, bipolar-type organics could utilize negatively or
positively charged states to interact with the cations or anions
mentioned above, which extends their applications to lithium ion
batteries (LIBs), electrochemical capacitors, and even dual-ion
batteries.
tetraaminephthalocyanine
(CuTAPc)
shows
multifunctional
applications in various energy storage systems, including lithium-
based DIBs using CuTAPc as the cathode material, graphite-based
DIBs using CuTAPc as the anode material and symmetric DIBs
using CuTAPc as both the cathode and anode materials. Notably, in
lithium-based DIBs, the use of CuTAPc as the cathode material
Porphyrin and phthalocyanine, typically planar aromatic
macrocyclic molecule, show bipolar features of donating or
-
1
-1
results in a high discharge capacity of 236 mAh g at 50 mA g and
accepting electrons, and their 18 π-electrons can be oxidized or
-
1
-1
[8]
a high reversible capacity of 74.3 mAh g after 4000 cycles at 4 A g . reduced into 16 π-electrons or 20 π-electrons, respectively.
Most importantly, a high energy density of 239 Wh kg and power
-
1
Moreover, their small HOMO-LUMO gaps can assist in the facile
injection and removal of electrons, resulting in fast redox
kinetics.[ In addition, the highly stable C-N bonds in their
frameworks can endow them with a high reversible capacity and
large working voltage.[7c] In this context, the development of
-
1
density of 11.5 kW kg can be obtained in all-organic symmetric
DIBs.
9]
Organic compounds are famous for their structural diversity,
which can be tailored by simply adding, removing, or substituting
functional groups.[1] In fact, even a simple functional group has
its own function that affects the properties of organic compounds,
which endows them with design flexibility for various applications.
porphyrin/phthalocyanine-based derivatives or polymers as
[10]
electrode materials for EESs has been reported.
However,
there are still several limitations on their synthesis and
electrochemical performance. For example, simplifying the
synthetic method needs to be addressed for their practical
application. Furthermore, the relatively high molecular weight
resulting from the inactive linking groups reduces the capacity of
porphyrin-based polymers.
[
2]
Undoubtedly, this structural diversity is necessary to optimize
organic compounds as electrode materials for electrochemical
energy-storage systems (EESs).[3] For example, the
incorporation of electron-withdrawing/donating groups could
elevate/reduce the redox potentials,[4] or the formation of
polymers could suppress the dissolution of small molecule
compounds.[ In addition, organic compounds are available in
natural resources or can be synthesized by relatively moderate
synthetic routes, thus showing environmentally friendly features
and minimal environmental footprints.[6] From the perspective of
sustainability, organic electrode materials are promising
alternatives to conventional transitional metal-based electrode
materials that are mined from minerals or synthesized using high
temperature.
To overcome these issues, we demonstrate that
metallophthalocyanine derivatives can be successfully served as
electrode materials for EESs. Herein, a molecular-level design
strategy is presented to screen high-performance and easily
synthesized phthalocyanine-based electrode materials. As a
result, the Cu tetraaminephthalocyanine (CuTAPc) possesses
bipolar and self-polymerized features. Interestingly, polymeric
phthalocyanine can be formed by the electropolymerization of
CuTAPc without the need for additional linking groups, resulting
in high capacity and improved cycling stability. Most importantly,
the bipolar feature endows CuTAPc with multifunctional
applications, including lithium-based and graphite-based dual
ion batteries (LDIBs and GDIBs), and symmetric dual ion
batteries (SDIBs). To the best of our knowledge, there are
scarce reports on bipolar redox organics as high-performance
electrode-active material in DIBs, let alone all-organic symmetric
DIBs.
5]
To date, various types of organic electrode materials based on
the different redox reactions, including n-, p-, or bipolar-type,
[
[
a]
b]
Dr. H. Wang, Dr. L. Wu, Y. Liu, Dr. Y. Wang, Prof. S. Song and Prof.
H. Zhang
State Key Laboratory of Rare Earth Resource Utilization,
Changchun Institute of Applied Chemistry, Chinese Academy of
Sciences, Changchun 130022, Jilin (China)
Phthalocyanines are centrosymmetric planar 18 π-electron
aromatic macrocycles with four nitrogen-linked isoindole units
that have a central cavity that can bind various metal ions to
E-mail: songsy@ciac.ac.cn
Dr. H. Wang, H. Wang, Prof. Dr. Z. Si, Q. Li, Q. Wu and Q. Shao,
School of Materials Science and Engineering, Changchun University
of Science and Technology, Changchun 130022, Jilin (China)
form metal phthalocyanines.[8] As
a
proof-of-concept
demonstration, the structure of CuTAPc as well as its two-
electron oxidation (+2 charge state) and two-electron reduction
Supporting information for this article is given via a link at the end of
the document.
(
-2 charge state) are shown in Figure 1a. Notably, 18 π-electron
phthalocyanine can be oxidized into dicationic species (+2
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COMMUNICATION
charge state, 16 π-electrons) or reduced into dianionic species (-
2
the electropolymerization process are shown in Supporting
Information).[11] An irreversible oxidation peak at approximately
0.35 V is observed in the CV curves of CuTAPc, which weakens
and disappears during cycling (Figures S7); however, other
phthalocyanine derivatives show reversible redox peaks during
the first and subsequent cycles (Figures S8), indicating the
oxidative electropolymerization of CuTAPc. In addition, ex situ
FTIR can confirm the formation of polymeric CuTAPc due to the
charge state, 20 π-electrons), respectively.[10a,10c] To
investigate the oxidation/reduction process of CuTAPc, density
functional theory (DFT) is used to calculate the HOMO/LUMO
energy levels (Figure S1). Clearly, CuTAPc has a very low
LUMO energy level that endows it with good oxidizability and a
high reduction potential and a small LUMO-HOMO gap that
endows it with good electronic conductivity and fast redox
kinetics.[4f,5d] These features enable CuTAPc to be a bipolar-type
electrode material, which can utilize its negatively or positively
2
absence of the characteristic peaks for -NH (Figure S9).
Intuitively, the glassy carbon electrode is coated by a blue-black
film that is visible to the naked eye after cycling only for CuTAPc
(Figure S10), which confirms the formation of the polymer. In
addition, DFT is also used to calculate the HOMO/LUMO energy
levels of CuTAPc dimer (Figure 2c). Compared with the CuTAPc
monomer, the CuTAPc dimer shows a decrease in the LUMO
energy and an increase in the HOMO energy. The smaller
LUMO-HOMO gap indicates increased electronic conduction,[
indicating that CuTAPc could show enhanced electrical
conductivity after the initial cycle.
+
+
+
+
charged states to interact with cations (Li , Na , K or H ) or
-
anions (PF
6
-, ClO
4
-, BF -
4
or TFSI ), respectively. Encouraged by
its redox mechanism, different polarity-switchable cells are
designed and constructed (Figure 1b). Coupled with a counter
electrode (Li foil), CuTAPc can be used as a cathode material in
LDIBs (cell 1) or an anode material in LIBs (cell 2). Interestingly,
coupled with graphite or itself, CuTAPc could be assembled into
GDIBs (cell 3) or SDIBs (cell 4).
9]
Figure 1. (a) Two-electron oxidation (+2 charge state) and two-electron
reduction (-2 charge state) of CuTAPc. (b) Various cell configurations for using
CuTAPc as a bipolar electrode material.
Figure 2. (a) Molecular structure of the various phthalocyanine derivatives. (b)
-
Geometry of PF
6
binding to CuTAPc. (c) Energy level diagrams of CuTAPc
and its dimer obtained from DFT calculations.
To screen high-performance phthalocyanine-based electrode
materials, we design and synthesize two categories of
phthalocyanine derivatives with different central metal ions, such
as none, Cu, Fe, or Co, and different substitutional groups, such
The electrochemical properties of CuTAPc as the cathode
material in cell 1 are investigated in detail. During the charge
process, CuTAPc can be oxidized into a dicationic species
2 2
as none, -NO , -NH , -OH, or -N=C-Ph (Figure 2a, detailed
2
+
-
(
CuTAPc , 16 π-electrons) that could capture PF
6
from the
synthesis and characterization of these compounds are shown
in Supporting Information and Figure S2). To compare the
effects of the different functional groups, their electrochemical
performance in cell 1 is investigated. By contrast, CuTAPc
+
electrode; at the same time, the Li from the electrolyte could
move to the anode. Conversely, during the discharge process,
CuTAPc2+ is reduced into electrically natural CuTAPc, or even
2
-
-
the dianionic species (CuTAPc , 20 π-electrons), and then PF
6
shows the optimal cycling performance (Figure S3), which could
+
-
dissolve back into the electrolyte to react with the Li released
be attributed to the strong interaction between CuTAPc and PF
6
[
7c,12]
from the anode to form stable LiPF
6
.
This hypothesis can be
(
Figure 2b) and the electropolymerization of the CuTAPc
verified by ex situ FTIR, element mapping and XPS analysis
(Figure S11-S13). To confirm the redox reaction, cyclic
voltammograms (CVs) are obtained (Figure 3a). During the first
anodic scan, an obvious irreversible oxidative peak can be
observed at 3.6 V. After the first anodic scan, the highly
reversible CV curves remain. These results are in accordance
with the irreversible feature observed in the three-electrode
monomers (Figure S4). On one hand, the high binding energy of
-
-
(
4.72 eV suggests the stronger affinity of CuTAPc toward PF
6
Figure S5). On the other hand, this transformation from
monomeric CuTAPc to polymeric CuTAPc could be preliminary
verified by ex situ FTIR analysis (Figure S6). To further confirm
this transformation, the electropolymerization of CuTAPc is
performed using a three-electrode system (detailed methods for
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system, which further confirms the self-polymerizing feature of
CuTAPc. Furthermore, the charge/discharge curves and the
corresponding dQ/dV curve also show similar features (Figure
show good Li+ storage properties (Figures S17-S21).
Furthermore, coupled with graphite, CuTAPc could be
assembled into asymmetric GDIBs (cell 3), which also delivers
good energy storage properties (Figure S22-S23). CV curves of
GDIBs show three pairs of oxidation/reduction peaks,
3b and Figure S14a). In addition to the irreversible initial charge
capacity, CuTAPc could deliver high charge/discharge
-1
corresponding to the different interaction processes of PF
6
-/Li+
capacities of 300 and 236 mAh g , respectively, along with a
-1
[12a,14]
Coulombic efficiency (CE) of 78.8% at 50 mA g . Herein, carbon
black shows the negligible capacity contribution (Figure S14b).
Interestingly, the charge/discharge capacities of 112.9/112.3
mAh g-1 at 300 mA g-1 are retained after 200 cycles (Figure 3c).
into/out of the graphite/CuTAPc (Figure S24).
In cell 3,
CuTAPc as the anode material could experience both the
reduced (n-doped) and oxidized (p-doped) state, that is, a
2-
2+
-
transformation from [CuTAPc] to [CuTAPc] , during which PF
6
-1
+
At a high current density of 4 A g , CuTAPc also displays high
initial charge/discharge capacities of 192.9/151.9 mAh g-1 and
maintains high charge/discharge capacities of 74.3/75.4 mAh g-1
after 4000 cycles (Figure 3d). Even at a very high current
and Li from the LiPF
6
electrolyte could insert/deinsert graphite
and CuTAPc, respectively (for details, see the Supporting
Information). This hypothesis could be further confirmed by XRD
patterns, element mapping and XPS analysis (Figure S25-S27).
-1
density of 20 A g , CuTAPc delivers a high reversible capacity
of 109 mAh g-1 (Figure 3e). Moreover, after back and forth deep
cycling over 300 cycles, a high reversible capacity of 155.4 mAh
g-1 is recovered when the current density is returned to 1 A g-1.
Obviously, CuTAPc shows an excellent rate capability, which
could be attributed to the reduced charge-transfer resistance
(
Figure S15). To further reveal the reasons for the high-rate
capability, a detailed kinetic analysis was conducted by CV
[
13]
curves at various scan rates (Figure 3f).
Based on the
b
equation i = av , the b values, an indicator of the electrochemical
behavior, are determined to be 0.997 and 0.996 (Figure 3g).
Herein, the b value approaches 1.0, indicating a capacitive
-
mechanism of PF
6
storage for CuTAPc. The capacitive
contribution can be quantitatively determined; for example,
CuTAPc shows 92.57% of the capacitance contribution at a
scan rate of 0.6 mV s-1 (Figure S16). The capacitive contribution
increases from 84.43% to 99.23% as the scan rate increases
from 0.2 to 1.0 mV s-1 (Figure 2h), indicating a capacitive
mechanism, especially at high rates.
-
1
Figure 4. (a) CV curves of the SDIB in the range of 4.0-1.0 V at 0.1 mV s . (b)
Charge/discharge profiles of the SDIB (the inset shows that a coin full cell can
light a small LED lamp). (c) Cycling performance of the SDIB at 0.2 A g . (d)
Ragone plots of cell 1, cell 3 and cell 4.
-
1
To completely demonstrate the bipolar feature of CuTAPc, a
symmetric system using CuTAPc as both the cathode and
anode materials was constructed. CV curves are first used to
explore the fundamental electrochemical properties of the
symmetric system (Figure 4a), which shows no well-defined
voltage plateau, suggesting rapid multiple redox reactions from
the oxidized (p-doped) and reduced (n-doped) state, that is, a
transformation from [CuTAPc]2+ to [CuTAPc]2- (for details, see
the Supporting Information).[7c] The typical charge/discharge
curves show a broad operating voltage window and a similar
voltage profile as the CV curves (Figure 4b). Interestingly, the
SDIBs can light two-series-connected LEDs (inset of Figure 4b).
In addition, the SDIBs show initial charge/discharge capacities of
-1
1
33.2/110.9 mAh g-1 at 0.2 A g along with a CE of 83.2% and a
-1
high reversible capacity of 60.1 mAh g after 200 cycles with a
capacity retention of 54.2% (Figure 4c). Moreover, even at very
Figure 3. Electrochemical performance of CuTAPc as the cathode material in
-
1
cell 1. (a) CV curves in the range of 4.5-1.5 V at 0.1 mV s . (b) Charge-
-1
high current density of 10 A g , GDIBs delivers a high reversible
-
1
-1
discharge curves at 50 mA g and cycling performance at 0.3 A g (c) and 4 A
g
capacity of 22.5 mAh g-1 (Figure S28), indicating the superior
rate performance. Furthermore, cell 1 shows a high specific
-
1
(d). (e) Rate performance at various current densities. (f) CV curves at
different scan rates. (g) the corresponding plots log(i) versus log(v) at each
redox peak and (h) contribution ratio of the pseudocapacitance at various scan
rates.
energy of 454 Wh kg-1 and a specific power of 38.4 kW kg , cell
-1
-1
3
shows a high specific energy of 719.5 Wh kg and a specific
power of 18.3 kW kg , while cell 4 shows a high specific energy
of 239 Wh kg-1 and a specific power of 11.5 kW kg-1 (Figure 4e),
-1
To confirm the bipolar feature, CuTAPc is used as the anode
material to construct conventional LIBs (cell 2), which could
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COMMUNICATION
which can even compete with organic-based batteries[7c,10c,12b]
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In summary, for the first time, our findings confirm that
CuTAPc exhibits bipolar and self-polymerized features, which
can be used as the electrode materials for DIBs, including all-
organic symmetric DIBs. Coupled with
a lithium counter
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-
1
-1
a high reversible capacity of 74.3 mAh g after 4000 cycles at 4
-1
A g . More encouragingly, coupled with graphite or itself,
CuTAPc could be assembled into asymmetric and symmetric full
cells; for example, symmetric full cells could display a high
[
[
6]
7]
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Acknowledgements
The authors are grateful for the financial aid from the National
Natural Science Foundation of China (Grant Nos. 21590794,
2
1771173, 21521092 and 51502284), K. C. Wong Education
Foundation (GJTD-2018-09), the Science Technology
Department of Jilin Province (Grant No. 20170101177JC,
0170101186JC and 20180101179JC), and the CAS-CSIRO
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Keywords: phthalocyanine derivatives • self-polymerization•
bipolar organics • all-organic symmetric batteries • dual ion
batteries
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Angewandte Chemie International Edition
10.1002/anie.201904242
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
A
bipolar and self-polymerized
Heng-guo Wang, Haidong Wang,
Zhenjun Si, Qiang Li, Qiong Wu, Qi
Shao, Lanlan Wu, Yu Liu, Yinghui
Wang, Shuyan Song* and Hongjie
Zhang
phthalocyanine complex is used as
the polarity-switchable and high-
performance electrode material for
lithium-based and graphite-based dual
ion
batteries,
even
all-organic
symmetric dual ion batteries. This
work can bridge the gap between
organic batteries and dual ion
batteries.
Page No. – Page No.
A
bipolar and self-polymerized
phthalocyanine complex for fast and
tunable energy storage
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