A large π-conjugated tetrakis (4-carboxyphenyl) porphyrin anode enables high specific capacity and superior cycling stability in lithium-ion batteries

Article abstract of DOI:10.1039/c9cc05474j

We demonstrated a novel single molecule-tetrakis(4-carboxyphenyl) porphyrin (TCPP) with a large π-conjugated system as a high-performance organic anode of lithium batteries. It was found that this TCPP displayed relatively low solubility (<0.1 mg mL^-1) in a 1 M LiDFOB/PC electrolyte, high reversible specific capacity (ca. 1200 mA h g^-1 at 358 mA g^-1), excellent rate capability (548.4 mA h g^-1 at 8 A g^-1) and superior cycling performance (capacity retention of 89percent after 2500 cycles at 6 A g^-1).

Full text of DOI:10.1039/c9cc05474j

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S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
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DOI: 10.1039/C9CC05474J
ARTICLE
Large π-conjugated tetrakis (4-carboxyphenyl) porphyrin anode
enables high specific capacity and superior cycling stability in
lithium-ion battery
Received 00th January 20xx,
Accepted 00th January 20xx
a,b,=
b,=,
b
b
b
b
a
Han Wu , Jianjun Zhang *, Xiaofan Du , Min Zhang , Jinfeng Yang , Jinning Zhang , Ting Luo ,
DOI: 10.1039/x0xx00000x
a
a,
b,
Hao Liu , Hai Xu *, Guanglei Cui *
We demonstrated a novel single molecular-- tetrakis(4-carboxyphenyl) increased molecular weight. For organic electrode rely on functional
porphyrin (TCPP) with large π-conjugated system as high-performance group to store Li-ion, large π-system always means lower reversible
organic anode of lithium batteries. It was found that this TCPP displayed capacity. Increasing the molecular polarity by introducing functional
11
relatively low solubility (<0.1 mg / mL) at 1 M LiDFOB/PC electrolyte, high groups was also a favourable solution. Liu and his group found that
reversible specific capacity (ca. 1200 mA h g-1 at 358 mA g ), excellent rate phenazine (PNZ) delivered a much better cycle performance (86%
capability (548.4 mA h g-1 at 8 A g ) and superior cycle performance after 100 cycles) by introducing two amino functional groups 2,3-
-1
-1
-
1
(
capacity retention of 89 % after 2500 cycles at 6 A g ).
diaminophenazine (DAP). The introduction of functional groups can
dramatically change electron cloud distribution of molecular and the
solubility of organic molecules, then affected the electrochemical
performance of anode.
Lithium ion batteries (LIBs) have become the main power of multi-
functional portable devices such as smartphone, laptop and
electronic watch. While the large-scale applications of
commercialized LIBs using conventional inorganic electrodes were
limited by their low energy density and poor rate performance.
1
Recently, a kind of structures with large π-system has been
attracted a lot of attention of scientists. Porphyrin-derived molecules
have substantial advantages in modifying the structure to improve
2-3
What’s worse, commercial inorganic electrodes usually contain
12-13
the insolubility and high electric conductivity.
And a highly stable
4
harmful chemical particles (i.e. cobalt) , which can contaminate
14-15
porphyrin-derived cathode has been reported for LIBs.
While in
5
-6
natural environment and threat human health.
this work, CuDEPP was relatively hard to synthesis, and the other
material discussed in this paper, CuTPP is easy to obtain, but its high
soluble in organic electrolyte resulted in poor battery performance.
Inspired by this work, we considered that porphyrins may work as a
great anode material due to its high electrochemical stability and
large π-conjugated. Furthermore, porphyrins generally possess small
In order to tackle abovementioned problems, organic
electrodes with flexible structural diversity seem to be one of the
best candidates for conventional inorganic electrodes owing to their
7
non-reliance on rare materials, infinite availability from easily
accessible natural sources and biomass, well-known redox stability.
However, there are critical issues that need to be addressed for the
8
practical application of organic electrodes. For the past few
decades, plenty of efforts have been devoted to address these
9
problems. Expanding π-conjugated system has been approved to be
an effective way to enhance electrical conductivity and suppress the
1
0
dissolution of inorganic electrodes in electrolyte. Masaru Yao et al
compared two kinds of organic electrodes (9,10-anthraquinone (AQ),
and 5,7,12,14-pentacenetetrone (PT)), reached a conclusion that PT
with larger π-conjugated system exhibited better cycling stability
than that of AQ. Enlargement of the π-system can be an effective way
to suppress the dissolution of electrode and d to improve their cycle
stability. While enlarging the π-system always accompany with
a
College of Chemistry and Chemical Engineering, Central South University,
Fig. 1 Difference in absorbance at 658 nm of (a) bare TCPP in 1 M
LiDFOB/PC with vary concentration, (b) TCPP discs in 1 M LiDFOB/PC
after different times, (c) UV-VIS spectrum of pure TCPP in 1 M
LiDFOB/PC, (d) UV-VIS spectrum of TCPP anodes in 1 M LiDFOB/PC.
Changsha 410083, P. R. China
Qingdao Industrial Energy Storage Technology Institute, Qingdao Institute of
Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao
b
2
66101, P. R. China.
†
Electronic Supplementary Information (ESI) available: Experience section and
supplementary figures. See DOI: 10.1039/x0xx00000x
These authors contributed equally to this work.
=
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was part of capacity provided by Super P, so it was need to further
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DOI: 10.1039/C9CC05474J
discussion the exact number which inserted into TCPP. As we above-
mentioned, that Super P can form a plateau around 1.7 V, so we
assumed that this part of capacity was not provided by the reaction
of TCPP. We believe that there were two steps in the whole reaction
process. As indicated in Fig. 4c, the first step was Li-ion inserted into
-1
porphyrin ring which displayed a capacity of ca. 652 mA h g , this
+
step was from A to B (from 1.4 to 0.35 V), which equal to 20 Li . And
+
second step was Li reacted with benzene (from 0.35 V to 0.01V), This
-1
+
step can provide ca. 800 mA h g , which amount to ca. 24 Li .
To gain further insight into the Li-ion insertion–deinsertion
mechanism within TCPP, ex situ FTIR before and during the first
discharged and charged processes were carried out. All the sample
were dismantled from batteries at different DOD and SOC of A, B, C,
and D as above described. As shown in Fig. 4d, the absorbance signal
Fig. 3 Electrochemical performances of the TCPP acid anode in the
voltage range of 0.01-3.0 V. (a) cycle performance and Coulombic
-1
efficiency of TCPP/Li battery at 6 A g , typical SEM images of (b) Rate
capability of TCPP/Li battery at room temperature, (c) Comparison in
electrochemical performance indices.
-
1
at ca. 1788 cm attribute to the vibrational modes of the C=O (in the
red dashed frame), and it was barely no change during the whole
-
1
charge/discharge process except slightly shifted to 1760 cm when
discharged to 0.01 V, implying the carbonyl has not reacted with Li-
ion, and the change of the wavenumber were caused by the
anode can delivery ca. 1200 mA h g-1 at 358 mA g-1 after 200 cycles,
which was much higher than those of most previously reported
organic electrodes and commercial inorganic anodes (i.e. graphite).
And its’ cycling stability was also favourable. At a high charge rate of
transformation of π-conjugate system. the absorbance signals at ca.
-1
1
020 cm (in the cyan dashed frames) associated with the vibrational
-
1
6
A g , it still exhibited superior capacity retention (80.5% after 3000
cycles).
In order to correctly assess the performance of TCPP anode, we
of porphyrin do not significantly change from 3 to 1.4 V, when
discharged to 0.35 V, the intensity peak vanish and blended into a
-1
-1
board signal from 900 cm to 1100 cm , further discharged to 0.01
V, the peak became even boarder, after recharged to 3 V, this peak
did not fully recover. This phenomenon testified that the lithium
reacted with porphin were during the voltage range of 1.4 to 0.35 V,
while also indicated that this reaction was not completely reversible
And It may be contributed to the low columbic efficiency. Both
also compared this anode with other recently reported organic
electrode. Among all the anodes in the Fig. 3c and Table SІ, TCPP has
the longest cycle life, the most favourable rate performance except
maleic acid. And the discharge capacity at low rate was only lower
than PDA derivative, Maleic acid and PIAQ, it is much higher than
other anodes.
-1
-1
absorbance signals at ca. 1602 cm and ca.1400 cm (in the green
Electrochemical impedance spectroscopy (EIS) studies were
performed after different cycles, and the corresponding results were
portrayed in Fig. 4a. By comparison, the overall impedance of the
TCPP electrode after 100 cycles was significantly lower than those of
2
1-22
many other reported organic electrodes in the literature.
This
explained the superior high rate capability. It was worth noted that
the diameter of the semicircle after 10 cycles was extremely high,
while as the cycles continued, the impedance decreased at first 100
cycles, which associated with the increasing capacity of TCPP anode.
Also, it should be mentioned that the diameter of the semicircle
showed only a slight increase from 100 to 200 cycles. This implied
that the particle surface of the TCPP was stable after 100 cycles. A
slight increase of charge - transfer resistance was believed to be
associated with the evolution of the electrode − electrolyte
interface.
To investigate the Li storage mechanisms of the TCPP and the
amount of Li-ion insertion in a single discharge process during
different voltage, the first discharge / charge process was been and blue dashed frames) were characteristic absorption of benzene.
systematic researched. All the samples were retrieved from the
dismantled cells at different depth of discharge (DOD) and state of Fig. 4 (a) EIS measurements of the TCPP electrode after different
charge (SOC) states (see Fig. 4b). As it was shown in Fig. 4b, A, B, C, cycles, (b) nyquist plots at different DODs and SOCs in the first cycle,
D represented different DOD and SOC of discharge to 1.4 V, 0.35 V, and (c) purposed mechanism of lithiation/delithiation for TCPP
.01 V and charge to 3 V. It gave a discharge capacity of 1702.5 mAhg- anode. (d) FTIR spectra of pristine TCPP anode, discharged to1.4 V,
0
1
.
Considering that for one molecule of TCPP reacted with one Li-ion 0.35 V, 0.01 V, and charged back to 3.0 V in the initial cycle. (e) Ex-
-1
contributed a theoretical capacity of ca. 33.5 mA h g , the above data situ XRD patterns of TCPP before and after the first discharge
shown that each TCPP molecule can accept 50 Li-ions. While, there process.
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J. Name., 2013, 00, 1-3 | 3
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These two signals were stable before 0.35 V, indicating that Li-ion China (No. 2018YFB0104300), Think-Tank Mutual FunVdiewoAfrtQiclienOgndlainoe
were not inserted into benzene at this voltage range. When Energy Storage Industry Scientific ResearDcOh,I: 1K0e.1y03S9c/iCe9nCtiCfi0c54a7n4dJ
discharged to 0.01 V, the signal became smoother and barely Technological Innovation Project of Shandong (No. 2017CXZC0505).
disappear. While when recharged to 3 V, the signals reappeared.
These changes verified our assumptions made before that the
reaction between Li-ion and benzene were happened at 0.35 to 0.01
Conflicts of interest
V.
There are no conflicts to declare.
As Li ion insertion will induce a change in the crystalline state of
the electrode materials, an ex situ X-ray diffraction (XRD) study was
also performed to characterize the crystal structure changes in TCPP
before cycle and at different discharge/charge voltage of A, B, C, D
shown in Fig. 4e and Fig. S12. As displayed in Fig. S12, the sample
before cycle shown a three sharp and intensify peaks at about 43.4°,
Notes and references
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50.6° and 74.2°, these peaks were belonging to the Cu current
collector. These three peaks at same position during the whole
discharge/charge process eliminate the variation caused by the
experiment conditions. More details are shown in the Fig. 4e, and
there are also three relatively small peaks at around 39.5°, 65.4° and
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72.6°, these peaks are ascribed to TCPP. When discharged to point A,
the sample remained stable, not notably change was detected,
indicating that the structure remained stable during this process.
After discharged to point B, there was an obvious bump show up
from 40° to 80° which manifested the formation of amorphous
phases, and at the same time the peak around 39.5° become
smoother while the peak around 65.4° unchanged. The loss of
crystallinity was attributed to Li ion insertion in condensed aromatic
7
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structures
and/or to organic compound swelling by the
2
4
electrolyte. These changes accorded with assumptions made
before that Li-ion only react with porphin at voltage range 3 to 1.4 V.
However, when discharge potentials decrease to 0.01 V, the peak
around 69.5° vanished while the overall picture has remained stable.
Furthermore, these two peaks both slightly changed their position,
which also indicated the variation of π-conjugate system. After
recharge to 3 V, the peak around 69.5° reappear and bump become
smaller indicating that the structure can partly restore and
suggesting the good stability of TCPP anode.
1
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We have demonstrated a novel molecule TCPP with large π-
conjugated structure as promising anode for high-performance
lithium-organic batteries. The large π-conjugated system and four
carboxylates of TCPP largely suppress the dissolution of anode
material in electrolytes. It was also found that TCPP anode delivered
1
1
1
1
2
2
2
2
2
-
1
-1
a specific capacity of 1200 mA h g at 358 mA g , which was much
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1
higher than those of commercial anode (i.e. 370 mA g for graphite)
and most of reported organic electrodes. In addition, even at 6 A g ,
it still possessed superior cycling stability (capacity retention of 80.5
-1
%
after 3000 cycles). Highly stable structure and unique lithium-ion
storage mechanism is the key point of this excellent battery
performance. By means of ex-situ FITR and XRD, we also purposed a
two- step mechanism of lithiation/delithiation reaction for TCPP. All
these fascinating results endow this organic small molecular with
large π-conjugated system a very promising organic electrode
materials with superior battery performance and insolubility for
high-performance lithium-organic batteries.
This original research was financially supported by the National
Natural Science Foundation of China(Nos. 51703236 and U1706229),
the National Science Fund for Distinguished Young Scholars (No.
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Graphical abstract
The small HOMO–LUMO gaps that enable the facile uptake and release of electrons, which can improve rate capability.
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