Journal of Power Sources 436 (2019) 226848

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Journal of Power Sources

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Pyromellitic dianhydride: A new organic anode of high electrochemical

performances for lithium ion batteries
Ruitian Guo a, Yan Wang a, **, Shuai Heng a, Guobin Zhu a, Vincent S. Battaglia b,
Honghe Zheng a, *
a
College of Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou, Jiangsu, 215006, PR China
b
Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA, 94720, United States

H I G H L I G H T S

� Pyromellitic anhydride is firstly adopted as the anode of lithium-ion batteries.

� Ultra-high capacity and rate capability of the pyromellitic anhydride anode are obtained.
� No obvious capacity loss is observed after 500 charge/discharge cycles.
� The underlying mechanisms for lithium storage are discussed.

A R T I C L E I N F O A B S T R A C T

Keywords: Organic energy storage materials attract extensive attention as a potential alternative for the next generation of
Lithium ion battery lithium ion batteries. However, most of the reported organic electrodes can not achieve a good balance among
Pyromellitic anhydride high capacity, high rate and long cycle-life. In this work, pyromellitic anhydride is adopted as a new anode
High electrochemical performance
material for lithium-ion batteries. It exhibits superior electrochemical performances compared to most of the
Mechanism
reported organic electrodes. The pyromellitic anhydride anode is able to reversibly deliver a capacity of
1472.2 mAh g 1 at 30 mA g 1. Even at an extremely high current of 30 A g 1, the electrode still retains
562.7 mAh g 1. After a 500 electrochemical cycles at 150 mA g 1 charge and 600 mA g 1 discharge, almost no
capacity loss can be observed. The good electrochemical performance of the pyromellitic anhydride anode is
because of its excellent lithium conductivity capability, as well as the stable solid electrolyte interface film
formed on the electrode.

1. Introduction critical issue of pulverization and poor conductivity, as well as a huge

Lithium ion batteries (LIBs), as the advanced rechargeable batteries,
are the dominant mobile power sources for portable electronic devices.
Nowadays, with the wide application of LIBs in electric vehicles and
smart grids, high security and sustainability are required for modern
LIBs with high energy and power density [1]. However, traditional LIBs
can hardly meet these requirements due to their limited capacity and the
moderate rate performance of the widely adopted commercial graphite
materials [2]. To break these limitations aroused from graphite anodes,
it is imperative to develop new anode materials. Among various anode
materials, metal oxides have been widely studied because of the high
capacity around 600–1000 mAh g 1 [3]. These substances have the
irreversible capacity loss in the first cycle [4,5]. In recent years, silicon
anode attracted wide attention of researchers as it has an extremely high
theoretical capacity of 4200 mAh g 1, which is ten times higher than
that of graphite. However, silicon suffers from a huge volume change
(400%) upon electrochemical cycles [6]. Although much effort has been
made to solves these problems, the progress seems to be sluggish, the
rate capability and cycling behavior are still not satisfactory and the
large-scale application of silicon material into commercial LIBs still has a
long way to go [7,8].
Organic compounds are eco-friendly with the major composition of
carbon, oxygen, nitrogen and hydrogen, which have received great
attention as active electrode materials for lithium storage. Different with

* Corresponding author.
** Corresponding author.
E-mail addresses: wang_yan@suda.edu.cn (Y. Wang), hhzheng@suda.edu.cn (H. Zheng).

https://doi.org/10.1016/j.jpowsour.2019.226848
Received 21 May 2019; Received in revised form 25 June 2019; Accepted 2 July 2019
0378-7753/© 2019 Elsevier B.V. All rights reserved.
R. Guo et al. Journal of Power Sources 436 (2019) 226848

Fig. 1. Electrochemical performances of the PMDA anode in the voltage range of 0.01–3.0 V: (a) cyclic voltammograms; (b) the initial five charge and discharge
profiles at 30 mA g 1; (c) the rate capability at 30 mA g 1 charge and various discharge rates and (d) the corresponding discharge profiles; and (e) the cycling and
coulombic efficiency cycled at 150 mA g 1 charge/600 mA g 1 discharge after five cycles at 30 mA g 1 (the inset is cycled at 60 mA g 1 after rate test).

inorganic substances, organic compounds are featured with structural
diversity, environmental friendliness, renewability and design flexibility
[9]. Driven by these considerations, many organic electrode materials
have been studied and reported in recent years. However, most of them
are adopted as the positive electrode materials with moderate electrode
potential. By contrast, the studies of organic compounds as anode ma­
terials with low electrode potential are not too much [10]. Even so,
significant progresses have been achieved in this field, especially for
high capacity and high power purposes. Wang et al. [11] proposed
polytetra(2-thienyl)ethylene as the LIB anode material. It exhibits a high
capacity of 973 mAh g 1 at 100 mA g 1 and it retains 468 mAh g 1 at
1 A g 1 current density. Poly(3,30 -bithiophene) was reported by Zhang
et al. [12], which exhibits a discharge capacity of 1215 mAh g 1 at
45 mA g 1. At a current density of 5 A g 1, it can still deliver a capacity
of 387 mAh g 1. Wang [13] et al. reported maleic acid anode exhibits an
ultrahigh reversible capacity of ca. 1500 mAh g 1 at 46.2 mA g 1, and
the electrode still delivers a capacity of 570.8 mAh g 1 at 46.2 A g 1.
Although with high reversible capacity, it must be noted that the first
coulombic efficiency (CE) for all the reported organic compounds are
very low. Most of the reported CE values fall in the range between 40
and 50% [13–15]. There is no doubt, the low CE severely hinder the
development and application of the high capacity organic compounds
into LIBs. It is known that more than 85% of the first CE is essential to
avoid high reversible lithium loss in the cell formation. Nevertheless,
rare work has been attempted to get a high first CE for organic anode
materials.

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R. Guo et al.
In this report, we adopted pyromellitic anhydride (PMDA) as the
anode material for LIBs. There are a benzene ring and four symmetrical
carboxylic acid groups in PMDA, which can undergo chemical reactions
such as esterification, acid chloride, hydrogenation, amidation, imid­
ization, purification and others. PMDA is an important raw material for
organic synthesis and a basic raw material for the development of new
chemical materials, widely used as precursors for diverse plastics,
binders, explosives/propellants, films, and coatings [16]. However,
although academics and industry show a strong interest in this material
and have conducted extensive research, its lithium storage properties
and the corresponding mechanisms have never been systematically
studied.
With this material as the anode material for LIBs, it is interesting to
obtain a high specific capacity with ultrahigh rate capability and
excellent cycling stability. When cycled at 30 mA g 1 between
0.01–3.0 V vs. Li/Liþ, the reversible capacity is obtained to be as high as
1600 mAh g 1. More importantly, a much enhanced first CE of 68.4% is
obtained. Even at 30 A g 1, the PMDA anode still retained a high ca­
pacity of 562.7 mAh g 1. During 500 cycles at 150 mA g 1 charge and
600 mA g 1 discharge rate, the electrode retained a high specific ca­
pacity of ca. 900 mAh g 1 without obvious capacity fading. The lithium
storage mechanisms of the PMDA are investigated by X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (FTIR), Raman and X-
ray photoelectron spectroscopy (XPS) studies.
2. Experimental
2.1. Electrode preparation
The PMDA anode was prepared by the following four steps. Firstly,
composite PMDA (Aladdin), acetylene black (AB, Denka Singapore
Private Co., Ltd.), sodium carboxymethyl cellulose (CMC-Na, 2 wt%)
and styrene-butadiene copolymers (SBR, 40 wt%) at the weight ratio of
5:4:0.5:0.5 in deionized water. Secondly, the slurry is homogenized with
a FA25 superfine homogenizer (at the rotating speed of 4000 rpm for
30 min). Thirdly, the uniform slurry is cast onto 15 μm-thick Cu foil by a
doctor blade, and dried under 60 � C. Finally, the obtained electrode
laminate was rolled out with a rolling machine to enhance the adhesion
between the active material and the current collector. The electrode is
punched out into circle discs of 13 mm diameter and further dried in
vacuum at 120 � C for 12 h. At the same time, the AB anode (AB:CMC:
SBR ¼ 4:0.5:0.5 wt%), PMDA anodes with different AB contents (PMDA:
AB:CMC:SBR ¼ 6:3:0.5:0.5 wt% and 7:2:0.5:0.5 wt%) and PMDA anode
with Super P (SP) as conductive agent (PMDA:SP:CMC:
SBR ¼ 5:4:0.5:0.5 wt%) were also prepared according to the same pro­
cedure. Besides, PMDA-graphite composite anodes were prepared with
the same procedure, in which graphite are artificial graphite (AGP-8)
and natural graphite (918) obtained from Shenzhen Beterui New Energy
Materials Group Co., Ltd. The weight ratio of PMDA:graphite:AB:CMC:
SBR is 5:1:3:0.5:0.5. The active material loadings of all the anode lam­
inates are controlled around 0.4 mg cm2.
2.2. Battery assembly and testing
The electrochemical properties for the anode materials were deter­
mined in 2032 coin cells, in which lithium foil (thickness: 0.3 mm, China
Energy Lithium Co., Ltd.) is used as the counter electrode. The coin cells
were made in an Ar-filled glove box with water and oxygen contents
below 0.5 ppm. The electrolyte adopted 1 M LiPF6 in a mixture of
ethylene carbonate (EC)/ethyl methyl carbonate (EMC)/dimethyl car­
bonate solution (EC/EMC/DMC, v/v/v ¼ 1:1:1). The Celgard 3501 is
used as the separator.
The galvanostatic charge/discharge tests were conducted on Maccor
S4000 (Maccor Instruments, USA) at 30 � C condition. Five formation
cycles were charged/discharged at 30 mA g 1 between 0.01 V and 3.0 V
vs. Li/Liþ. Rate capability were compared at 30 mA g 1 charge
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Journal of Power Sources 436 (2019) 226848
(lithiation) and various discharge (delithiation) rates of 30 mA g 1,
150 mA g 1, 300 mA g 1, 600 mA g 1, 1.5 A g 1, 3 A g 1, 6 A g 1,
15 A g 1 and 30 A g 1, respectively. The cycling stability of the anode
was evaluated at different charge and discharge rates. All the specific
capacities (mAh g 1) obtained for PMDA/AB/PMDA-graphite anodes
are based on the active material mass. Cyclic voltammetry (CV) of the
anode was performed on an Autolab potentiostat (PGSTAT302 N,
Autolab Instruments, Switzerland) in the voltage range of 0.01–3 V vs.
Li/Liþ at 0.1 mV s 1 scan rate. The electrochemical impedance spec­
troscopy (EIS) of the PMDA anode was recorded by an electrochemical
work station (Zahner Elektrik IM6) in the frequency of 100 kHz-10 mHz
with an alternating voltage of 5 mV.
2.3. Electrode characterization
XRD (PANalytical X’Pert PRO, Netherlands) patterns were collected
between 10 and 60� with an increment of 6 min 1. Raman spectroscopic
studies were carried out (JobinYvonLabRAM HR 800) with a 632.8 nm
excitation laser. FTIR (Tensor 27, BRUKER OPTICS, Germany) was
employed to characterize the structure of the PMDA electrodes at
different depth of discharge (DOD) and state of charge (SOC) in the first
cycle. The structural evolution of the PMDA anode at different electro­
chemical stages was also analyzed with ex-situ XPS (Thermo Fisher
spectrometer).
3. Results and discussion
3.1. Electrochemical properties of the PMDA anode
The electrochemical properties of the PMDA anode are displayed in
Fig. 1. Fig. 1a shows the CV curves of the PMDA anode between 0.01 and
3 V at a scan rate of 0.1 mV s 1. During the first cathodic process, there
are four peaks located at 2.31, 1.61, 0.85 and 0.28 V, respectively. The
weak peak at 2.31 V gradually shifts to a higher potential and the peak
intensity gets stronger in the following cycles, which reaches 2.54 V in
the fifth cycle. The wide and large peak at 1.61 V in the first cycle is not
visible in the second cycle, indicating it is an irreversible process. The
peak at 0.85 V also disappeared in the second cycle. This is often
observed for organic anodes relating to the formation of solid electrolyte
interface (SEI) [17,18]. Meanwhile, a new peak at 0.96 V emerged in the
second cycle which is quite stable in the following cycles. The peak at
0.28 V shifts to lower potential in the following cycles, and reaches
0.17 V in the fifth cycle. From the CV curves, the peaks at 2.54, 0.96 and
0.17 V are the reversible lithiation process for the PMDA anode. During
the first anodic process, two peaks at around 0.95 and 2.48 V are
observed, and the first peak shifts to 1.16 V in the second cycle. There­
after, both the peaks at 1.16 V and 2.48 V show good reversibility in the
following cycles, showing a reversible lithium storage property of the
PMDA anode.
Fig. 1b exhibits the initial five charge/discharge profiles of the PMDA
anode at 30 mA g 1. In the first cycle, the charge and discharge capacity
was obtained to be 2153.6 and 1472.2 mAh g 1, respectively. The ob­
tained first CE for the compound is 68.4%, significantly higher than the
ca. 50% reported in literature for different other organic compounds
used for LIBs [13–15]. The 31.6% capacity loss is ascribed to the two
irreversible processes at around 1.96 V and 1.10 V, which are well
consistent with CV results. The first irreversible process is ascribed to the
structure transformation of the electro-active material, which will be
discussed later. The second irreversible process is attributed to the for­
mation of SEI layer at the electrode/electrolyte interface. Besides, it
should be noted that the addition of high content of the conductive
carbon (AB) is another factor for the initial low first CE for the PMDA
anode. Fig. S1a shows that the first CE of 43.7% is obtained for the AB
anode (AB:CMC:SBR ¼ 4:0.5:0.5 wt%). However, we can not do without
AB in the PMDA anode as it is an important electrode component to
ensure a good electronic conductivity of the electrode laminate (see
R. Guo et al.
Fig. 2. (a) EIS measurements of PMDA electrodes under different DODs and SOCs in the first cycle at 30 mA g 1 and the corresponding Nyquist plots; and (b) PMDA
electrodes selected for EIS measurements after different cycles at 30 mA g 1 and the corresponding Nyquist plots.
Fig. S2). The importance of a sufficient amount of conductive agent for
the PMDA electrode can also be demonstrated by Fig. S3. As can be seen,
with increase of AB content, the capacity of the PMDA anode increased,
this is because a sufficient amount of AB could provide enough active
sites for PMDA, which is benefit for the increase of the electrode ca­
pacity. However, it is well known that adding a large amount of AB will
result in a decrease in electrode energy density. At this point it is worth
mentioning that compositing PMDA with graphite is an efficiency
method to decrease the AB content without sacrifice the electrode ca­
pacity (see Fig. S4), and the detailed work will be published by us in the
near future. In the second cycle, the reversible capacity of the PMDA
anode increased to 1535.1 mAh g 1 and the CE reached to 92.5%. In the
subsequent cycles, the reversible capacity slightly increases, which gets
to 1593.6 mAh g 1 with the CE of 97.8% at the fifth cycle. Besides, the
PMDA anode also exhibits a high capacity ca. 1600 mAh g 1 when SP is
used as a conductive agent (see Fig. S5). The reversible capacity of the
PMDA anode is obtained to be significantly higher than most of the re­
ported organic anodes for LIBs [11,12,19,20], and is almost four times
higher than the theoretical capacity of graphite (372 mAh g 1). The
obtained reversible capacity in this work is also considerably higher
than most of the reported metal oxides anodes in literature [21,22].
Fig. 1c shows the rate performance of the PMDA anode at 30 mA g 1
charge and various discharge rates. At the current density of 1.5, 3 and
6 A g 1, the reversible capacity is 1311.8, 1179.9 and 939.1 mAh g 1
respectively. Even at 15 and 30 A g 1, the PMDA anode is still able to
deliver a high capacity of 704.7 and 562.7 mAh g 1, respectively. While
the capacities of the AB anode are around 322 mAh g 1 at low current
densities (150–600 mA g 1) and decreased with the increase of the
current densities (see Fig. S1b), indicating AB particles only contribute a
small part of capacity to the PMDA anode, and the high capacity of the
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Journal of Power Sources 436 (2019) 226848
PMDA anode is mainly due to the excellent lithium storage performance
of PMDA. The obtained rate capability of the PMDA anode, is superior to
most of the reported organic and inorganic anodes [11,12,23,24].
Fig. 1d shows discharge profiles of the PMDA anode at different cur­
rents. It can be seen that, at 150–600 mA g 1, the electrode displays the
typical discharge plateaus of the PMDA. At 1.5–3 A g 1, the discharge
plateaus of the PMDA anode still can be clearly observed except a slight
elevation, which mainly due to the polarization resulting from the in­
ternal resistance of the cell. When the discharge current exceeds
15 A g 1, the potential will rise quickly to the cut-off potential due to Li
ion diffusion limitation in the electrode. But it should be noted that, even
at 30 A g 1 (corresponding to ca. 80C for graphite anode), a high ca­
pacity of 562.7 mAh g 1 can still be delivered, showing an excellent
lithium transmission for the PMDA anode.
The long-term cycling behavior for the PMDA anode is displayed in
Fig. 1e. When cycling at 150 mA g 1 charge/600 mA g 1 discharge, the
electrode capacity exhibits an increase in the initial 20 cycles. The slight
capacity increase is believed to be associated with the activation of the
PMDA electrode. After 500 cycles, almost no capacity fading can be
detected and the electrode retained a high reversible capacity of
878.2 mAh g 1. When cycled at a low current density of 60 mA g 1, a
reversible capacity of 1100.8 mAh g 1 was obtained after 200 cycles.
Under different cycling conditions, no capacity decrease can be observed
during the long-term cycling test. Besides, at the stable cycling stage, the
CE is higher than 99.0% for each cycle, exhibiting a good reversibility of
the PMDA anode. The very stable cycle behavior is another striking
advantage for the PMDA anode compared to the reported organic
electrodes in literature [25,26].
EIS studies were carried out under different electrochemical stages.
Fig. 2a shows the Nyquist plots of the PMDA anode at different DOD and
R. Guo et al. Journal of Power Sources 436 (2019) 226848

Fig. 3. (a) XRD and (b) FTIR spectra of the pristine PMDA anode laminate (black line), PMDA powder (red line) and PMA powder (blue line). (For interpretation of
the references to colour in this figure legend, the reader is referred to the Web version of this article.)

SOC states in the first cycle. At open circular voltage (OCV) state (A), one
semicircle in the high-to-medium frequency region appeared, reflecting
the interfacial impedance (RSEI) between the electrode and the electro­
lyte. When charged to 1.5 V (B), the semicircle diameter is significantly
decreased, which may be due to the increase of the conductivity of the
electrode because of lithiation. When charged to 0.5 V (C), another
semicircle appeared in the intermediate frequency region, representing
the charge transfer at the electrode surface (Rct). Both the two
semicircles are increased at 0.01 V (D). Afterwards, when the electrodes
are discharged to 1.5 and 3 V (E and F), respectively, the electrode
impedance is continuously decreased. It should be noted that compared
to the electrode at OCV state (A), the resistance of the PMDA anode
significantly reduced after the first cycle (F), indicating an “active pro­
cess” happened during the first cycle. Fig. 2b shows the Nyquist plot of
the PMDA electrode at fully discharge state with different electro­
chemical cycles. Clearly, the overall impedance of the electrode has

1
Fig. 4. (a) Points selected for FTIR measurements during the first charge and discharge at 30 mA g ; (b) FTIR spectra of the pristine PMDA electrode; FTIR spectra of
the PMDA electrode at different (c) SOC states and (d) DOD states in the first cycle.

5
R. Guo et al.
Fig. 5. (a) Points selected for XPS measurements during the first charge and discharge at 30 mA g 1; XPS spectra of (b) C 1s and O 1s, (c) Li 1s of PMDA electrodes at
different electrochemical states; and (d) area ratios of Li 1 s/C 1s peaks and Li 1s/O 1s peaks.
barely changes with cycle number during the initial five cycles, indi­
cating a stable SEI film formed during the first cycle.
3.2. Lithium storage mechanisms for the PMDA anode
To characterize whether PMDA is hydrolyzed into pyromellitic acid
(PMA) during the slurry preparation, XRD and FTIR spectra of the
pristine PMDA anode laminate, PMDA powder and PMA powder are
compared. Fig. 3a shows the XRD patterns. As shown in this figure, for
the pristine PMDA anode, there are four obvious peaks at 11.7, 16.0,
25.1 and 26.1� , respectively. All these peaks are consistent well with the
typical peaks of PMA powder at 11.9, 16.1, 25.0 and 26.2� , respectively.
Even the weak peaks of the PMDA anode laminate at 13.2, 18.4, 22.4
29.1 and 32.0� are kept well with PMA powder. The XRD spectra indi­
cate that PMDA is hydrolyzed into PMA during the slurry preparation.
FTIR spectra can further confirm this conclusion. As shown in Fig. 3b, for
the PMDA powder, the characteristic peaks at 1859 and 1769 cm 1 are
attributed to the C–– O stretching vibration of the O– – C–O–C– – O group
[27], the other two obvious peaks at 1236 and 917 cm 1 assigned to
C–O–C asymmetric and symmetric stretching vibration of anhydride,
respectively [28]. For the PMA powder, the significant peak at
1713 cm 1 is the C– – O stretching vibration of COOH [29]. We can see
that the characteristic peaks of the PMDA anode laminate are not
consistent with PMDA powder but quite similar with PMA. Besides, in
order to eliminate the influence of conductive agent and binder, we
prepared a PMDA film containing only PMDA, the fabrication process of
PMDA film is exactly the same as that of PMDA anode, except that PMDA
film was prepared on the glass. Fig. S6 compares the XRD and Raman
spectra of the PMDA powder, PMA powder and PMDA film, we can see
that the characteristic peaks of PMDA film are consistent well with the
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Journal of Power Sources 436 (2019) 226848
PMA powder. All these results indicate PMDA is hydrolyzed into PMA
during slurry preparation.
To investigate the lithium storage mechanisms of the PMDA, Fig. 4
shows the ex-situ FTIR spectra of the PMDA anode. Fig. 4a shows the
selected DOD and SOC states in the first cycle. Fig. 4b displays the FTIR
spectra of the pristine PMDA electrode. The peak at 1707 cm 1 is
assigned to C– – O stretching vibration of COOH [29], the band at
1609 cm 1 and 1415 cm 1 are designated to the antisymmetric and the
symmetric stretching vibrational mode of O– – C–O [30]. Fig. 4c shows
the FTIR spectra of the PMDA electrode at different SOC states in the first
cycle. For the electrode charged to 1.5 V (B), the two distinct peaks at
1577 and 1381 cm 1 proved the formation of the carboxylic acid salt
(COOLi) [31], while both of the two peaks are significantly decreased
when charged to 0.5 V (C), which completely disappeared when charged
to 0.01 V (D). For the electrode charged to 0.5 V (B), the three dominant
peaks at 1509, 1434 and 866 cm 1 appeared, the first two peaks
correspond to the C– – O stretching modes of Li2CO3, the last peak is
ascribed to the δ(CO23 ) mode [32], and all these three peak are signif­
icantly enlarged when charged to 0.01 V (D). These peaks are corre­
spond to the components of SEI layer. Fig. 4d shows the FTIR spectra of
the PMDA electrode at different DOD states in the first cycle. Obviously,
the peaks at 1509, 1438 cm 1 and 863 cm 1 retain stable during
discharge process, indicating a stable SEI film formed during the first
charge process. It should be pointed out that two peaks at 1618 and
1389 cm 1 gradually appeared during discharge process, indicative the
recovery of the COOLi.
Fig. 5 shows the ex-situ XPS spectra of the PMDA anode for further
investigating the lithium storage mechanisms. Fig. 5a shows the samples
taken from the cells at different DOD and SOC states for XPS test. Fig. 5b
shows the corresponding C1s and O1s spectra. As shown in this figure,
R. Guo et al. Journal of Power Sources 436 (2019) 226848

Fig. 6. C 1s XPS spectra of the (a) PMDA powder with fitted components, and the PMDA electrode with fitted components (b) at OCV state, (c) charged to 0.01 V, and
discharged to (d) 3 V.

there are significant differences in the spectra of both C1s and O1s
collected under various electrochemical conditions, demonstrating the
structural change of PMDA during the first charge and discharge pro­
cess. Fig. 5c shows the corresponding Li1s spectra. It can be seen that no
Li1s signal was detected for the electrode at OCV state, while the in­
tensity of the Li1s peak increased during charging, and decreased during
discharging. At fully discharge state, the Li1s peak is still evident
because of the irreversible reaction during the first charge process, this is
consistent with CV and the first charge and discharge profiles. Fig. 5d
shows the area ratios of both Li1s/C1s and Li1s/O1s. Clearly, the rela­
tive content of lithium increases with charge and decreases with
discharge, verified the reversibility of lithium storage in PMDA
electrodes.
Fig. 6 presents the C1s-fitted XPS spectra of the PMDA powder and
the PMDA anode at OCV state, charged to 0.01 V and discharged to 3 V
in the first cycle. For the PMDA powder (Fig. 6a), the C1s peaks with
binding energy of 292.0, 289.8, 289.0, 286.3, 285.7, and 285.1 eV are
attributed to π-π*, C(O)O, C– – O, C–O, C–C/C–H and C– – C bond,
respectively [33,34]. For the fresh PMDA electrode (Fig. 6b), there are
five peaks at 289.2, 288.0, 285.9, 284.3, and 284.1 eV from high to low
binding energy. It’s clearly to see that the fitted C1s peaks of the PMDA
electrode at OCV state are not consistent well with the PMDA powder,

Scheme 1. The proposed lithium storage mechanism for the PMDA anode.

7
R. Guo et al.
but similar with PMA powder (see Fig. S7). This further verified that
PMDA hydrolyzed into PMA. When charged to 0.01 V (Fig. 6c), C– –C
peak centered at 284.1 eV disappeared while C(O)O peak centered at
289.2 eV is greatly increased. When discharged to 3 V (Fig. 6d), the C––C
peak appeared again, and the intensity of the C(O)O peak decreased. All
these results reflect that the C– – C and C(O)O bonds are the primary
active sites for reversible storage of lithium.
To clearly reveal the lithium storage mechanisms of the PMDA,
Scheme 1 is proposed. As shown in this scheme, PMDA is hydrolyzed
into PMA during slurry preparation, this is verified by XRD, FTIR and
XPS spectra (see Figs. 3, 6, S6 and S7). During the initial charge process,
four carboxyl hydrogen atoms of PMDA are irreversibly replaced by two
lithium ions, which is verified by FTIR spectra in Fig. 4c; then a four-
electron reduction reaction happens on the four carbonyl groups, and
another six-electron reduction happens on the benzene ring. Thus, a
total fourteen electrons are involved in the electrochemical reactions.
The carbonyl groups and the benzene ring are the active site for lithium
storage sites are not only verified by ex-site XPS study (Fig. 6), but also
verified by other researchers. Numazawa [19] reported the hetero­
aromatic ring and carbonyl substituent could reversible storage lithium
ions. Wang [11] reported thiophene units can be act as the reversible
redox reactions in lithium/sodium ions storage. Cui [35] proposed 3,4,9,
10-perylenetetracarboxylic dianhydride could inserted sixteen lithium
ions because lithium ions can be inserted into both of the carbonyl ox­
ygens and the unsaturated carbons of the C6 aromatic rings. According
to the calculation formula of the theoretical specific capacity of an
electrode material [36], fourteen electron transfers based on PMA
structure corresponds to a theoretical specific capacity of 1477.2 mAh
g 1, which is lower than the obtained specific capacity of 2153.6 mAh
g 1 for the PMDA electrode during the first charge. This may be related
to the conductive carbon and the surface adsorption of lithium also
contribute the large capacity to the PMDA anode.
4. Conclusion
In summary, we found that PMDA anode exhibits high reversible
capacity, high power and long cycle life as LIB anode. It attains a high
reversible capacity of ca. 1600 mAh g 1 at 30 mA g 1 charge and
discharge, which is four times higher than the theoretical capacity of
graphite. Even at 30 A g 1, a high discharge capacity of 562.7 mAh g 1
can still be obtained. The PMDA anode also keeps a high capacity of
878.2 mAh g 1 at 150 mA g 1 charge/600 mA g 1 discharge even after
500 electrochemical cycles. No detectable capacity loss is seen during
the long-term cycles. All these results show that PMDA has great po­
tential for use as LIB anode. The excellent lithium conductivity and the
stable SEI film formed on the electrode explain the good electrochemical
performances of the PMDA anode.
Acknowledgements
This work was financially supported by the funding of the National
Natural Science Foundation of China (NSFC, contract no. 21875154 and
21473120) and 863 project of the Department of Science and Technol­
ogies, China (contract no. 2015AA034601).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2019.226848.
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