Electrochimica Acta 434 (2022) 141306

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Electrochimica Acta
journal homepage: www.journals.elsevier.com/electrochimica-acta

Columnar liquid-crystalline triazine-based dendrimer with carbon

nanotube filler for efficient organic lithium-ion batteries
Febri Baskoro a, 1, Pin-Chieh Chiang a, 1, Yao-Chih Lu a, b, Jonathan N. Patricio c, d, Susan D. Arco c,
Hsieh-Chih Chen e, Wen-Shyong Kuo f, Long-Li Lai b, *, Hung-Ju Yen a, *
a
Institute of Chemistry, Academia Sinica, 128 Academia Road, Section 2, Nankang, Taipei 11529, Taiwan
b
Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., Puli, Nantou 545, Taiwan
c
Synthetic Organic Chemistry Laboratory, Institute of Chemistry, University of the Philippines Diliman, Quezon City 1101, Philippines
d
Materials Science and Engineering Program, College of Science, University of the Philippines Diliman, Quezon City 1101, Philippines
e
Department of Fiber and Composite Materials, Feng Chia University, Taichung 40724, Taiwan
f
Department of Aerospace and Systems Engineering, Feng Chia University, Taichung 40724, Taiwan

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

Keywords: Owing to their highly tunable molecular structure and chemical stability, dendrimers consisting of triazine and
Triazine piperazine moieties have been investigated. The present work describes the electrochemical performance of a
Dendrimer columnar liquid-crystalline triazine-based dendrimer containing the linker with diaminopropane (DAP) as a
Carbon nanotube
lithium-ion battery anode. To elucidate the impact of conductive carbon filler in the electrode, a tiny amount of
Anode
Li-ion battery
carbon nanotube (CNT) paper has been incorporated in the DAP anode. The battery performance revealed that
the DAP anode has shown a high specific capacity of up to 444 mA h g− 1 at 0.5 A g− 1 after 200 cycles. Sur­
prisingly, with an additional 1% CNT, the Li+ storage capacity of the dendrimer-based composite anode (DAP/
CNT1%) significantly enhanced up to 656 mA h g− 1. To the best of our knowledge, this is the first time that a
triazine-based dendrimer has been utilized as an anode material in conjunction with a small amount of CNT to
further boost its energy-storing capabilities through a synergy of capacitive storage mechanisms and improve Li+
transport. The efficient lithium storage of DAP/CNT composite further shows its amenability as organic electrode
material for next-generation organic Li-ion batteries.

1. Introduction
The reliance on nonrenewable fossil fuels as primary energy sources
has resulted in an enormous increase in global energy consumption, as
well as serious environmental issues. Therefore, renewable energy
sources such as wind, hydro, and solar energy are encouraged to address
the aforementioned challenges; nevertheless, these clean energy sources
are limited by geographical or natural constraints. In this light, the use of
effective energy storage technology becomes critical to ensuring a
steady supply of electricity [1,2]. Li-ion batteries (LIBs) have been
claimed to have promising qualities such as lightweight, high power and
energy densities, long cycle life, minimal self-discharging, and no
memory effect among energy storage technologies [3–6]. LIBs have been
widely used in a range of applications since their early commercializa­
tion in the 1990s, including portable electronics, electric vehicles (EVs),
and stationary utility storage [7–11]. The most crucial aspect of a bat­
tery assembly is selecting an electrode material with high electro­
chemical stability and appropriate energy levels for effective charging
and discharging [12,13]. In addition, the electrode material must be
able to maintain the battery for more than 1000 cycles.
In a traditional LIB, a positive electrode (cathode), a negative elec­
trode (anode), an electrolyte system, and a separator, that prohibits
physical contact between the two electrodes, are contribute to the
overall device performance. Particular interest on the anode materials,
graphite has been recognized as the most popular anode material in
battery assembly due to its excellent mechanical stability, electrical
conductivity, cost-efficiency, and widespread availability [14]. How­
ever, graphite-based anode cells experience poor charge/discharge sta­
bility, producing a substantially lower specific capacity after many
cycles than its theoretical capacity (372 mA h g− 1), prohibiting its use in

* Corresponding authors.
E-mail addresses: lilai@ncnu.edu.tw (L.-L. Lai), hjyen@gate.sinica.edu.tw (H.-J. Yen).
1
These authors equally contributed to this work.

https://doi.org/10.1016/j.electacta.2022.141306
Received 5 April 2022; Received in revised form 21 September 2022; Accepted 5 October 2022
Available online 6 October 2022
0013-4686/© 2022 Elsevier Ltd. All rights reserved.
F. Baskoro et al.
next-generation LIBs [7,14–16]. As a result, much research has been
conducted to produce ecologically acceptable and alternative electrode
materials to graphite with high energy density and exceptional stability
to meet the market demands for long-term energy storage. Over the last
three decades of LIBs development, functional ceramic materials such as
Si-based composites [17,18], Sn-based composites [19,20], and metal
oxide-based composites [21,22] have been widely investigated as anode
materials due to their relatively higher energy density. Despite its su­
perior energy storage capability, significant volume fluctuations of these
materials during lithiation/delithiation processes frequently resulted in
particle aggregation and stacked solid–electrolyte interphases (SEI)
layers on the electrode surface, resulting in rapid capacity fading
[23–25]. Additionally, the synthesis of the materials mentioned above
frequently necessitates multistep synthesis methods that consume a lot
of energy [26–29]. As a result, developing alternative materials with
high energy density and structural stability for LIB anode is critical and
urgent in order to meet the demand of energy storage.
On the contrary, organic materials have spurred interest as an
alternative electrode for next-generation LIBs due to their abundant
supply, low cost, structural variation, highly tunable electrical behavior,
and environmental inertness [30]. Apart from its benefits, organic anode
materials are prone to low conductivity and cycling stability due to their
high solubility in electrolytes, particularly for small organic molecules,
thus limiting total battery performance. Synthetic polymers and other
macromolecules are amongst the most versatile organic materials that
can be structurally tuned to prevent dissolution in nonaqueous elec­
trolytes while simultaneously improving electrochemical stability and
overall device performance [31]. The abundance of carbonyl and amino
functional groups, which are requisite for the formation of enolate
moieties, were already reported to potentially afford binding sites for
Li-ion intercalation, hence boosting the kinetics of redox processes [32].
In addition, series of novel conductive carbon fillers have been inten­
sively studied to improve electronic conductivity of electrodes materials
[33–35]. These conductive carbon fillers have been reported could serve
as establishing conductive interconnected network in the electrode, thus
improve Li+ transport and reduce internal resistant [36,37]. Among
conductive carbon fillers, carbon nanotubes (CNTs) and graphene are
considered to be promising candidates due to their high electrical con­
ductivity, and their capability in improving electrochemical perfor­
mance [33–35,37].
Dendrimers are highly ordered and polymeric molecules with a well-
defined, homogenous, and monodisperse structure. These macromole­
cules have symmetric tree-like arms or branching units that are radially
constructed around a small molecule or a linear polymer core and are
generally synthesized by stepwise assembly processes. Due to their
highly tunable molecular architecture, dendrimers have a range of
fascinating features, including polyvalency, self-assembly, electrostatic
interactions, chemical stability, minimal cytotoxicity, and solubility.
Because of their non-grained borders and regular alignments, an inter­
esting class of dendrimers has been reported to show columnar liquid­
–crystalline (LC) phases [38–41]. Furthermore, covalent triazine-based
frameworks have also been produced and studied for their ability to
accommodate guest molecules [42–45]. Triazine units in dendritic
frameworks, for example, have been found to have a strong π–π inter­
action with tetrafluoro benzoquinone in solution, implying that such
triazine moieties are suitable for the formation of LC phases upon
thermal treatment due to favorable face–to–face packing [38,42,43,
46–49]. Moreover, these unconventional covalent triazine-based
frameworks consisting of rigid cores, rigid linkages, and flexible pe­
ripheral chains are of interest in the field of triazine-based dendrimers
because their morphologies are controlled by restricted conformational
freedom; as with other dendritic systems, cavities can be created in the
dendritic frameworks to incorporate guest molecules or ions [40,41,50,
51]. These make dendrimers an intriguing choice of advanced functional
materials for the design and fabrication of high-performance electrode
materials for next-generation Li-ion batteries [39,52].
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Electrochimica Acta 434 (2022) 141306
In view of the requirement for innovative organic electrode mate­
rials, and in light of the previously reported studies, we report on the
electrochemical study of a columnar liquid-crystalline triazine-based
dendrimer with 1,3-diaminopropane as the central linker for LIB anode.
To improve electronic conductivity of dendrimer-based anode, CNT
paper was incorporated as conductive filler. Furthermore, the influence
of conductive CNT filler on the electrochemical performance of the DAP-
based LIB anode was also investigated.
2. Results and discussion
2.1. Materials characterization
The DAP dendrimer in this study was synthesized according to a
previous report [39]. Fig. 1a shows the chemical structure of DAP
dendrimer and a digital photograph of the as-prepared DAP powder for
LIB anode. Meanwhile, the scanning electron microscopy (SEM) of the
as-synthesized DAP is shown in Fig. 1b. The inset figure of Fig. 1b is the
magnification of the red-dashed square area. As can be observed in
Fig. 1b, the DAP sample exhibited a rough surface microstructure with
an asymmetric morphology. Further image analysis using ImageJ soft­
ware showed that an effective surface area of approximately 2022 μm2 is
estimated for DAP microparticle. (see Fig. S1, Supplementary Informa­
tion). Closer inspection reveals that the surface roughness is linked to
the existence of surface undulations, resulting in a macroporous struc­
ture which is beneficial for Li+ mobility during the lithiation process. To
verify the bulk porosity of DAP, we performed Brunauer− Emmett− ­
Teller (BET) measurement (Fig. S2). As shown in Fig. S2a, the
as-synthesized DAP exhibited type III adsorption-desorption isotherm
with a N2 adsorption capability of 63.10 cm3 g− 1 at 77 K, which further
indicates a mesoporous materials. Furthermore, the Bar­
rett− Joyner− Halenda (BJH) pore size distribution (Fig. S2b) confirmed
the formation of mesopores (2-50 nm) and macropores (50 nm <). In
agreement with surface porosity analysis, a broad diffraction peak at
around 21.49◦ is monitored in the X-ray diffraction (XRD) spectra,
indicating an amorphous structure of DAP at room temperature
(Fig. 1c). In addition, Fourier transform infrared (FT-IR) was employed
to characterize vibrational modes of the functional groups present in
DAP (Fig. 1d). As shown in Fig. 1d, two vibrational spectra attributed to
the N–H and sp3 C–H stretching were observed at 2921 and 2852 cm− 1,
respectively, which can be found on the central linker, branches, and
peripheral groups of the dendrimer structure (Fig. 1a). The intense
bands at around 1531 and 1476-1427 cm− 1 were associated with the
N–H and C–H bendings, while bands at around 1368, 1329, and 1255
cm− 1 were assigned to the aromatic C–N of the triazine and piperazine
moieties. However, a very weak vibrational spectrum is observed
around 1680 cm− 1, which was attributed to the C=N groups of the
triazine rings. A sharp vibrational band at around 1020 cm− 1 is moni­
tored and was ascribed to the C–N linkages between the triazine and
piperazine groups. Meanwhile, the vibrational band at 805 cm− 1 was
attributed to the C− H out-of-plane bending comprising the G3Cl den­
drons which further confirmed the successful formation of DAP.
2.2. Electrochemical performance of DAP-based anode
In this study, DAP dendrimer has been employed as LIB anode ma­
terial. A small amount of CNT paper, which is described in the Experi­
mental section, was further incorporated as conductive carbon filler to
form DAP/CNT1% composite anode. Both pristine-DAP and DAP/
CNT1% composite anode were then evaluated electrochemically in the
half-cell LIBs. To probe the redox potential of pristine-DAP and DAP/
CNT1% composite anodes, the cyclic voltammetry (CV) was performed
within the potential window of 0.02 to 3.0 V (against Li/Li+) at a scan
rate of 0.1 mV s− 1 (Fig. 2a). As depicted in Fig. 2a, three reduction peaks
at 1.89, 0.85, and 0.02 V on the cathodic scans, along with its oxidation
peaks on the anodic scans at 2.42, 1.02, and 0.12 V are observable for all
F. Baskoro et al. Electrochimica Acta 434 (2022) 141306

Fig. 1. (a) Chemical structure of DAP anode and its powder appearance. (b) SEM, (c) XRD, and (d) FT-IR characterizations of DAP.

Fig. 2. Electrochemical performance of DAP-based anode. (a) CV; (b) Galvanostatic profile; (c) Capacity profile at 0.5 A g− 1; (d) Rate performance.

four cycles. The first small reduction at 1.89 V along a shallow oxidation
potential at 2.42 V (inset Fig. 2a) could be ascribed to lithiation and
delithiation process of secondary amine. The reduction peak at 0.85 V on
the cathodic scan, and the oxidation peak at 1.02 V on the anodic scan
were attributed to the typical lithiation–delithiation process of C–
– N on
the triazine moieties in the DAP structure [53]. Meanwhile, the reduc­
tion and oxidation peaks at 0.02 V and 0.12 V, respectively, were
attributed to the typical Li+ insertion and de-insertion in other organic
moieties [27]. The formation of a SEI layer at the electrode− electrolyte
interphase as suggested by the cathodic peak at roughly 0.54 V was
observed during the 1st cycle (shown in black) [54,55]. Nonetheless, the
CV curves exhibited remarkable cyclic stability without any change for
each redox peak starting from the 2nd scan, demonstrating its structural
integrity during the electrochemical process. Interestingly, the inclusion
of 1% CNT as a filler resulted in an enhanced capacitance on the CV
curve (Fig. S2a), as evidenced by the increased area surrounded by the

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F. Baskoro et al. Electrochimica Acta 434 (2022) 141306

closed curve for DAP/CNT1% anode (red line) compared to that of

pristine-DAP (black line). Moreover, no significant change on the CV
curve for both pristine-DAP and DAP/CNT1% anode (Fig. S2a), indicates
that an additional 1% CNT did not tune the redox potential of DAP
during the lithiation/delithiation process.
To evaluate the Li+ storage capability, the half-cell was galvanos­
tatically charged–discharged using a constant current at a current den­
sity of 0.1 A g− 1 and a cutoff voltage window of 0.02–3.0 V against Li/
Li+. Fig. 2b shows the representative galvanostatic charge/discharge
profile of pristine-DAP anode over 100 cycles. During the first lithiation
process, a small irreversible plateau was observed at 0.54 V, corre­
sponding to a capacity loss of 20%, and could be attributed to SEI for­
mation derived from electrolyte decomposition during the initial
lithiation/delithiation process [27,56,57]. This observation is in good
agreement with that of the CV curve as shown previously in Fig. 2a.
Moreover, two well-defined reversible plateaus at 0.85 V and 0.02 V on
the lithiation process associated with effective Li+ insertion in the DAP
structure were maintained with excellent cyclic stability over the next
100 cycles. Remarkably, the specific capacity of the pristine-DAP
gradually increased from 444 mA h g− 1 (10th cycle) to 544 mA h g− 1
(100th cycle) at 0.1 A g− 1 (Fig. 2b). The higher specific capacity could be
due to better electrolyte penetration into DAP’s porous structure, which
increases the electrode’s wettability during cycling and maximizes the
number of Li+ binding sites. We believe this phenomenon is related to
the more conducive environment and improved electrode− electrolyte
interphase, which allows electrolytes to penetrate deeper into the anode
material, enhancing Li+ transport and creating additional pathways for
full utilization of triazine and piperazine group in the DAP structure as
Li+ binding sites.
In good agreement with the galvanostatic profile (Fig. 2b), the
pristine-DAP anode exhibited a maximum capacity of 567 mA h g− 1 at
0.1 A g− 1 current density with nearly 100% Coulombic efficiency (CE)
after 100 cycles (Fig. S3b). Furthermore, it is noteworthy that the
pristine-DAP anode could deliver a high capacity of 444 mA h g− 1 at a
high current density of 0.5 A g− 1, which is superior to commercial
graphite anode (198 mA h g− 1; Fig. 2c). Surprisingly, a significant ca­
Fig. 3. FT-IR spectra of DAP-based dendrimer at different stages.
pacity improvement is also monitored for DAP-based anode with an
additional 1% CNT at high current density (DAP/CNT1%; Fig. 2c). As
shown in Fig. 2c, DAP/CNT1% composite anode exhibited a gradual lithiation process in the functional groups of DAP-based anode. After the
increase from 485 mA h g− 1 to 656 mA h g− 1 at 0.5 A g− 1. This superior DAP-based anode was fully discharged at 3.0 V (green line), the vibra­
enhancement, which is even triple than that of commercial graphite, can tional spectra of N–H, sp3 C–H stretching, and C–N aromatic again
be ascribed to the intrinsically high conductivity of CNTs delivering a appeared in the FT-IR spectra (Fig. 3), suggesting a successful delithia­
synergistic effect on the macroporosity of DAP via interconnected net­ tion process. Additionally, new peaks associated with the formation of
works linking the triazine and piperazine moieties to the hexagonal carbonate anions (CO2− 3 ) were monitored in both the fully charged (0.02

honeycomb structure of sp2 carbon atoms for a more effective and
efficient Li+ transport and intercalation. Furthermore, as shown in
Fig. 2d, both pristine-DAP and DAP/CNT1% anode demonstrated an
excellent rate capability. The pristine-DAP anode delivered reversible
capacities of 420, 396, 359, 325, and 275 mA h g− 1 as the current
densities varied from 0.1, 0.5, 1.0, 2.0, and 5.0 A g− 1, respectively (black
line). Meanwhile, the composite DAP/CNT1% exhibited reversible ca­
pacities of 694, 537, 479, 421, and 348 mA h g− 1 as the current densities
varied from 0.1, 0.5, 1.0, 2.0, and 5.0 A g− 1, respectively (red line). The
excellent rate capability was demonstrated as a high capacity of 425 and
694 mA h g− 1 was recovered for pristine-DAP and DAP/CNT1% anode,
respectively, after the current density was reduced back to 0.1 A g− 1.
2.3. Li ion storage mechanism in DAP-based anode
In order to verify the Li+ storage mechanism in the DAP-based anode,
we employed the ex-situ FT-IR spectroscopy to evaluate the changes in
the functional groups at different stages (Fig. 3). As depicted in Fig. 3,
when the electrode was fully charged (0.02 V; blue line), the disap­
pearance of the vibrational spectra at 2921 and 2852 cm− 1, which are
attributed to the N–H and sp3 C–H stretching, as well as the missing
spectra of C–N aromatic can be observed, manifesting a successful
V) and discharged stages (3.0 V), which possibly indicated the formation
of an SEI layer on the DAP-based anode during the lithiation/delithia­
tion process. This also depicts that the Li+ insertion on the triazine and
piperazine played a major role in the battery performance.
In addition, according to Faraday’s law, the theoretical capacity of
the polymer-based anode can be estimated using the equation, C = nF/
3.6MW where C is the theoretical capacity, n is the accepted number of
electrons, F is the Faraday constant (96485 C mol− 1), and Mw represents
the molecular weight. As shown in Fig. 1a, if we assume that the lone
pair electron of nitrogen and the π electron could provide Li+ binding
sites, the DAP (Mw = 6022 g mol− 1) can accommodate approximately
160 Li-ions in its structure, which is largely due to Li+ insertion in the
triazine (5 Li+) and piperazine (6 Li+) groups. These 160 Li-ions in each
unit of DAP correspond to a theoretical capacity of approximately 712
mA h g− 1, which is consistent with our experimental result (Fig. 2c).
Therefore, based on our investigative analysis results, we proposed the
lithiation/delithiation reaction of DAP-based anode as presented in
Scheme 1. In addition, this superlithiation stage has also been reported
in several organic-based electrodes such as polymer-based anodes
[58–63].

4
F. Baskoro et al.
2.4. Charge storage behavior and kinetic studies of DAP-based anode
After monitoring the lithiation/delithiation process in DAP-based
anode, we performed charge storage evaluation and kinetical studies
to elucidate the role of CNT in the DAP-based anode. First, we used
sweep rate voltammetry at different scan rates in the potential window
of 0.02 to 3.0 V (against Li/Li+) to evaluate the charge storage mecha­
nism of DAP-based anode (see Fig. S4a and S4b). The sweep rate tech­
nique is a powerful method to probe the consecutive electrochemical
reactions occurring on the electrode material during the charge/
discharge process. In general, the total stored charge in a CV curve can
be classified into three components: (a) the faradaic contribution from
the diffusion controlled process (ion insertion); (b) the faradaic contri­
bution from the charge-transfer process with surface atoms, referred as
pseudocapacitance; (c) the non-faradaic contribution from the double
layer effect [29,64,65]. All of these faradaic contributions from diffusion
(insertion process) and capacitive effects can be stated by:
i = avb
where i is the current response to the scan rate v, while a and b are
constants. The b value can be obtained from the slope of log i vs log v. If
the b value is obtained close to 0.5, it indicates a half-infinite linear
diffusion-controlled process. However, when a b value is close to 1, it
suggests that the current generated is a surface-controlled process
(capacitive effects) [29,64–67]. As shown in Fig. S4, both pristine-DAP
and DAP/CNT1% exhibited reduce in specific current as the scan rate
was reduced from 1 to 0.1 mV s− 1. Interestingly, it is found that the b
value of DAP/CNT1% is slightly higher (0.78) than that of pristine-DAP
(0.68; Fig. 4a). This suggested that an additional 1% CNT (carbon filler)
in the DAP electrode significantly enhance capacitive effects.
Furthermore, the total charge stored for the capacitive (k1v) and
diffusion (k2v1/2) contributions at any fixed potential can be quantified
using the following formula [64,65,67]:
i = k1 v + k2 v1/2
Fig. 4. Charge storage mechanism of pristine-DAP and DAP/CNT1% at different scan rates. (a) Log peak current (i) against log scan rate (v) plot. (b) The i/v1/2 vs v1/2
plot. (d) and (e) Estimated diffusive and capacitive contributions of pristine-DAP and DAP/CNT1%, respectively, at various scan rates.
5
Electrochimica Acta 434 (2022) 141306
where k1 and k2 values can be determined by plotting i/v1/2 vs v1/2
(Fig. 4b). Fig. 4c and d depicted the capacitive and diffusion contribu­
tion of pristine-DAP and DAP/CNT1%, respectively. In good agreement
with the analysis of b value (Fig. 4a), the additional 1% CNT in the DAP
electrode increased the capacitive character (Fig. 4d) than that of the
pristine-DAP electrode (Fig. 4c). Initially, the pristine-DAP exhibited a
relatively high capacitive contribution approximately 55% at a high
scan rate (1–0.5 mV s− 1), and after the scan rate reduced to 0.1 mV s− 1,
this number gradually decreased up to 29% (Fig. 4c). On the other hand,
the DAP/CNT1% exhibited a higher capacitive behavior of 70% at a high
scan rate, then slightly reduced up to 43% at 0.1 mV s− 1 (Fig. 4d). This
suggested that a higher contribution of capacitive behavior could
possibly contribute to the increasing performance of DAP/CNT1% than
that of pristine-DAP (Fig. 2c and d). As the capacitive contribution was
improved, there are more Li+ can be adsorbed and then coordinated in
the DAP structure, thus further increasing the specific capacity. This
again suggests the potential of applying DAP/CNT1% as an efficient and
reversible anode material. As a brief summary here, our study has
demonstrated new pathways of fully utilizing the Li+ binding sites in
DAP/CNT1% composite electrodes. Both the triazine and piperazine
groups facilitate efficient and reversible Li+ storage inside the DAP
dendritic network via diffusion controlled process, while the sp2 carbons
arranged in a hexagonal honeycomb structure of CNT improve capaci­
tive behavior (surface controlled process). This behavior is depicted in
Fig. 2c, where the discharge capacity gradually increases after 100 cy­
cles, suggesting that the Li+ binding sites are optimized during the
cycling, and more efficient Li+ storage can be achieved due to better
electrolyte penetration inside of the DAP dendritic network.
To probe the kinetics phenomena at interphase and Li+ transport
inside the electrode, we employed electrochemical impedance spec­
troscopy (EIS) in the frequency ranged from 10 mHz to 1 MHz with an
AC amplitude of 10 mV to assess the electrochemical performance of the
battery anode comprising DAP-based dendrimer and the role of CNT
filler. Fig. 5 shows the Nyquist plots of the pristine-DAP and DAP/
CNT1% at different cycling intervals. Before cycling, both the pristine-
DAP and DAP/CNT1% exhibited two semicircles as shown in Fig. 5a;
F. Baskoro et al. Electrochimica Acta 434 (2022) 141306

Fig. 5. Nyquist plot of pristine-DAP and DAP/CNT1% at different cycling intervals: (a) before cycling, and (b) after 200 cycles at 0.5 A g− 1.

Scheme 1. Schematic Li+ storage mechanism in DAP-based dendrimer.

inset depicts the equivalent circuit model that was used to fit the Rctb of pristine-DAP significantly decreases from 270.4 Ω to 114.9 Ω
impedance data in the as-assembled state. The fitted parameters are when 1% CNT was added as a conductive filler. Notably, after 200 cy­
summarized in Table 1. As presented in Table 1, the bulk resistance (Rs) cles, both the DAP and DAP/CNT1% exhibited only one semicircle as
associated with the overall system resistance (the conduction through shown in Fig. 5b, indicating an improved material interphase inside of
electrolyte, separator, and wires) [68] only slightly changed during the the electrode during cycling thus minimizing inter materials
charging/discharging operation, indicating that DAP was highly stable charge-transfer resistance. Moreover, it is found that Rcta of
during electrochemical testing. This high stability further suggested low pristine-DAP significantly enhanced up to 298.9 Ω after 200 cycles,
interferences of conducting electrolytes, the separator, and testing wires while DAP/CNT1% significantly reduced to 151.8 Ω (Table 1). This is
during the electrochemical test. Additionally, there are two types of again associated with the intrinsically high conductivity of CNT deliv­
charge transfer resistance (Rct) in the mid-frequency region, which are ering a synergistic effect on the macroporosity of DAP via inter­
connected with the Li+ conduction across various interphases during connected networks linking the triazine and piperazine moieties to the
electrochemical operation: (i) electrode− electrolyte interphases (Rcta), hexagonal honeycomb structure of sp2 carbon atoms for a more effective
and (ii) material interphases inside of the electrode (Rctb). Although, the and efficient Li+ transport intercalation during charge/discharge
Rcta of the pristine-DAP electrode appears slightly lower (191.5 Ω) than process.
that of with additional 1% CNT (225.2 Ω) at before cycling (Table 1), the In addition, the Li+ diffusion analysis based on the Warburg
impedance element in the low-frequency region was performed for
pristine-DAP and DAP/CNT1% before and after 200 cycles. The War­
Table 1 burg impedance can be defined by:
Fitted data of EIS spectra of pristine-DAP and DAP/CNT1% before cycling and
after 200 cycles at 0.5 A g− 1. ′ σ σ
Z = 1 − j 1
ω2 ω2
Sample Stages Rs Rcta Rctb Diffusion
[Ω] [Ω] [Ω] coefficient
where Z´is the real impedance, ω is the angular frequency, and σ is the
[cm2 s¡1]
pristine- Before 4.177 191.5 270.4 2.16 × 10− 11 Warburg coefficient. The Warburg coefficient of pristine-DAP and DAP/
DAP cycling CNT1% before and after 200 cycles can be estimated by the slope of the
13
After 200 7.175 298.9 - 8.07 × 10− Warburg plot (Z′ against 11 ), which is presented in Fig. S5a and S5b,
cycles ω2
DAP/ Before 7.66 225.2 114.9 4.83 × 10− 11 respectively. Furthermore, the Li+ diffusion coefficient (DLi) was esti­
CNT1% cycling mated using the following equation:
12
After 200 4.448 151.8 - 1.20 × 10−
cycles

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F. Baskoro et al. Electrochimica Acta 434 (2022) 141306

( )
RT 1 4.2. Preparation of carbon nanotube paper (CNT paper)
σ= √̅̅̅
n2 F2 A 2 D1/2
Li CLi
The sizes of multi-walled CNTs are 100–120 microns in length and
− 1 − 1 30–40 nm in diameter. 50 mg CNTs were dispersed in the ethanol. A
where R is the molar gas constant (8.314 J mol K ), T is the absolute
magnetic stirrer was first used to mix CNTs within the solution, and a
temperature (K), A is the electrode area (cm2), n is the number of elec­
probe-type sonicator (1500 W, 20 kHz) was employed to disperse the
tron transfers, F is Faraday’s constant (96485 C mol− 1), and CLi is the
CNTs. The sonication time was 30 min. The CNT agglomerates were torn
concentration of ions (mol cm− 3) [69]. As presented in Table 1, DLi of
apart to become isolated CNT filaments. The CNT solution was then
DAP/CNT1% was found two times faster (4.83 × 10− 11 cm s− 1) than that
2

− 11 2 − 1 filtered by using a porous paper placed within a buffer container. A

of pristine-DAP (2.16 × 10 cm s ) at before cycling. After 200
cycles, the DLi indicates that Li+ mobility in the DAP/CNT1% was one
order magnitude faster (1.20 × 10− 12 cm2 s− 1) than that of pristine-DAP
(8.07 × 10− 13 cm2 s− 1). This kinetical phenomenon is in good agreement
with previous studies that the CNT as conductive filler could provide
conductive network which significantly improve Li+ transport and
reduce internal resistant [36,37]. Although, the DLi were relatively
slower in both pristine-DAP and DAP/CNT1% after 200 cycles. This
phenomenon is possibly due to the formation of SEI that minimized Li+
mobility [70,71].
In brief, the sweep rate CV and EIS studies revealed the importance of
additional CNT filler in DAP-based anode. As shown in Fig. 4c and d, the
sweep rate CV indicates additional 1% CNT tuned the charge storage
behavior of DAP-based anode by increasing capacitive contribution in
the Li+ storage mechanism. Furthermore, the EIS study unleashed that
the Li+ diffusion coefficient dramatically increase one orders of
magnitude for DAP/CNT1% compare with the pristine-DAP electrode
after 200 cycles (Table 1), implying an excellent Li+ transport during
charge/discharge cycling process thus result in significant increase Li+
storage capacity (Fig. 2c). This consistent with the previous study that
revealed a better Li+ transport could significantly enhance battery per­
formance [72]. We believe this phenomena are ascribed to highly
conducive CNTs which allows rapid electron transfer and enhancing Li+
transport, thus significantly improve the cycling performance of
DAP-based anode.
3. Conclusion
In this work, we developed a triazine-based dendrimer with 1,3-dia­
minopropane as the central linker and evaluated it as an anode material
for Li-ion batteries. The results indicated that pristine-DAP as an anode
material had a high specific capacity of 444 mA h g− 1 at 0.5 A g− 1, as
well as outstanding cycle stability, which might be attributed to its
molecular structure containing triazine and piperazine units. The in­
clusion of carbon filler (CNTs) resulted in a considerable capacity in­
crease of up to 656 mA h g− 1 at 0.5 A g− 1 after 200 cycles. Our study
suggests that the excellent electrochemical performance of the DAP/
CNT composite is primarily due to the dendrimer’s effective structural
design, which includes an uneven number of carbon atoms on the cen­
tral linker, as well as the added conductive network provided by CNTs,
resulting in high performance and long cycle life.
4. Experimental
4.1. Synthetic procedure of DAP dendrimer
The DAP dendrimer was synthesized following previous procedure
[39]. Briefly, 1,3-diaminopropane was allowed to react with one
equivalent of G3Cl dendron in dry tetrahydrofuran at 70 ℃ for 24 h. A
further equivalent of G3Cl was added, followed by 5 equivalents of po­
tassium carbonate, and the resulting mixture was reheated at 170 ℃ for
72 h in a sealed tube. The crude product was purified by chromatog­
raphy and recrystallization to afford the pure triazine-based dendrimer
(referred to as DAP) with a yield of 69%.
negative pressure was applied to the container to enhance CNT filtra­
tion. The deposited CNTs were re-integrated to become a film type. The
CNT paper with the filtering paper was dried at 50◦ C for 24 h. There­
upon the CNT paper was carefully peeled from the filtering paper. The
size of CNT paper was 10 × 10 cm and the thickness was about 0.18 mm.
The areal weight was 0.64 mg cm− 2. The CNTs in a CNT paper are
preferentially oriented along the in-plane directions. Compared with
their original forms of 3D irregular agglomerates, the CNT paper is flat,
flexible, self-standing and can be readily cut into size for application.
Because of the continuous network of CNT integration, the CNT paper
becomes much more electrically-conductive than the original CNT
agglomerates.
4.3. Characterization methods
X-ray diffraction (XRD) measurements were measured on a Bruker
D8 Advance X-ray Diffractometer at 40 kV and 40 mA using Cu Kα ra­
diation (λ = 1.5406 Å). Fourier transform infrared spectroscopy (FT-IR)
were measured on a FT/IR 6600, JASCO International Co., Ltd. Scanning
electron microscope (SEM) were performed using Field-Emission Scan­
ning Electron Microscope (FESEM), Ultra Plus - Carl Zeiss. The nitrogen
adsorption isotherms were measured at 77 K with an accelerated surface
area and porosimetry system, Autochem II 2920 (Micromeritics, Nor­
cross, GA). Prior to the analysis, the sample was degassed at 50◦ C for 12
h in a vacuum.
4.4. Coin cell preparation
To make the pristine-DAP anode, a homogeneous slurry mixture was
made by mixing 60% conductive carbon (Super P®; >99% (metal basis);
UBIQ Technology Co., Ltd), 20% as-synthesized DAP, 20% poly(vinyli­
dene fluoride) (PVDF; UBIQ Technology Co., Ltd) as a binder, and N-
methyl-2-pyrrolidone (NMP; Thermo Fisher Scientific) as solvent. The
slurry was cast onto Cu foil and dried on a hot plate at 94 ℃ for 12 h,
then for another 8 h at 80 ℃ in vacuo. A similar slurry process was used
to make the DAP/CNT1% anode, which consisted of 59% super-P, 20%
as-synthesized DAP, 1% CNT paper, 20% PVDF binder, and NMP as
solvent. For reference, a slurry consisting of 80% graphite (natural
graphite powder (GN-580L); UBIQ Technology Co., Ltd), 10% Super P,
10% PVDF, and NMP as solvent was also prepared. The pristine-DAP,
DAP/CNT1%, and graphite electrodes were cut (12 mm in diameter)
with an average loading of 0.138, 0.124, and 2.04 mg cm− 2, respec­
tively, before being placed in a glove box for coin cell production.
Finally, CR2032 type coin cells were fabricated in a high-purity Ar-filled
glove box (Vigor, Vigor Tech USA; H2O < 0.5 ppm, O2 < 0.5 ppm) using
the as-prepared DAP-based anode as a working electrode, Li metal foil as
a counter/reference electrode, Celgard 2325 as a separator, and 40 μL of
1 M LiPF6 in a 1:1 (v/v) ethylene carbonate/diethyl carbonate (EC/DEC;
UBIQ Technology Co., Ltd) as the electrolyte.
4.5. Electrochemical measurement
The cyclic voltammetry were performed using MultiPalmSens4
electrochemical analyzer, PalmSens BV at a scan rate of 0.1 mV s− 1
between 0.02 and 3.0 V. The electrochemical impedance spectroscopy
(EIS) analysis were conducted before and after battery cycle using CHI
electrochemical workstation model 760e, CH Instruments, Inc., with an

7
F. Baskoro et al.
alternating current (AC) voltage signal of 10 mV and frequency range
between 10 mHz to 1 MHz. The cells were charged and discharge gal­
vanostatically using AcuTech battery station systems (AcuTech Systems
Co. Ltd). Charge–discharge studies of the coin cells were performed by
using a programmable battery tester in constant current mode in the
potential range of 0.02 – 3.0 V. All measurements were conducted in
ambient condition.
Authors contributions
F.B. and P.-C.C. contributed equally. S.D.A., L.-L.L., and H.-.J.Y.
designed the experiments. Y.-C.L. and J.N.P performed the DAP syn­
thesis. F.B. and P.-C.C. performed the electrochemical and character­
ization experiments. H.-C.C. and W.-S.K. performed CNT paper
preparation. The manuscript was written and edited by F.B., J.N.P, S.D.
A., L.-L.L., and H.-J.Y. All authors discussed the results and reviewed the
manuscript.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
This work was financially supported by the Ministry of Science and
Technology in Taiwan (MOST 108-2113-M-001-023-MY3; MOST 110-
2124-M-001-001) and the Innovative Materials and Analysis Technol­
ogy Exploration in Academia Sinica (AS-iMATE-110-23).
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.electacta.2022.141306.
References
[1] D. Larcher, J.M. Tarascon, Towards greener and more sustainable batteries for
electrical energy storage, Nat. Chem. 7 (1) (2015) 19–29, https://doi.org/10.1038/
nchem.2085.
[2] Z. Yang, J. Zhang, M.C.W. Kintner-Meyer, X. Lu, D. Choi, J.P. Lemmon, J. Liu,
Electrochemical energy storage for green grid, Chem. Rev. 111 (5) (2011)
3577–3613, https://doi.org/10.1021/cr100290v.
[3] Z. Ba, Z. Wang, M. Luo, H.-b. Li, Y. Li, T. Huang, J. Dong, Q. Zhang, X. Zhao,
Benzoquinone-based polyimide derivatives as high-capacity and stable organic
cathodes for lithium-ion batteries, ACS Appl. Mater. Interfaces 12 (1) (2020)
807–817, https://doi.org/10.1021/acsami.9b18422.
[4] J.B. Goodenough, K.-S. Park, The Li-ion rechargeable battery: a perspective, J. Am.
Chem. Soc. 135 (4) (2013) 1167–1176, https://doi.org/10.1021/ja3091438.
[5] M. Li, J. Lu, Z. Chen, K. Amine, 30 years of lithium-ion batteries, Adv. Mater. 30
(33) (2018), 1800561, https://doi.org/10.1002/adma.201800561.
[6] G. Zubi, R. Dufo-López, M. Carvalho, G. Pasaoglu, The lithium-ion battery: state of
the art and future perspectives, Renew. Sustain. Energy Rev. 89 (2018) 292–308,
https://doi.org/10.1016/j.rser.2018.03.002.
[7] J.M. Tarascon, M. Armand, Issues and challenges facing rechargeable lithium
batteries, Nature 414 (2001) 359, https://doi.org/10.1038/35104644.
[8] B. Dunn, H. Kamath, J.-M. Tarascon, Electrical energy storage for the grid: a
battery of choices, Science 334 (6058) (2011) 928, https://doi.org/10.1126/
science.1212741.
[9] H. Lee, M. Yanilmaz, O. Toprakci, K. Fu, X. Zhang, A review of recent developments
in membrane separators for rechargeable lithium-ion batteries, Energy Environ.
Sci. 7 (12) (2014) 3857–3886, https://doi.org/10.1039/C4EE01432D.
[10] P.G. Bruce, B. Scrosati, J.-M. Tarascon, Nanomaterials for rechargeable lithium
batteries, Angew. Chem. Int. Ed. 47 (16) (2008) 2930–2946, https://doi.org/
10.1002/anie.200702505.
[11] T. Lei, W. Chen, W. Lv, J. Huang, J. Zhu, J. Chu, C. Yan, C. Wu, Y. Yan, W. He,
J. Xiong, Y. Li, C. Yan, J.B. Goodenough, X. Duan, Inhibiting polysulfide shuttling
8
Electrochimica Acta 434 (2022) 141306
with a graphene composite separator for highly robust lithium-sulfur batteries,
Joule 2 (10) (2018) 2091–2104, https://doi.org/10.1016/j.joule.2018.07.022.
[12] T. Lei, Y. Hu, W. Chen, W. Lv, Y. Jiao, X. Wang, X. Lv, Y. Yan, J. Huang, J. Chu,
C. Yan, C. Wu, X. Wang, W. He, J. Xiong, Genetic engineering of porous sulfur
species with molecular target prevents host passivation in lithium sulfur batteries,
Energy Storage Mater. 26 (2020) 65–72, https://doi.org/10.1016/j.
ensm.2019.12.036.
[13] W. Chen, T. Lei, C. Wu, M. Deng, C. Gong, K. Hu, Y. Ma, L. Dai, W. Lv, W. He,
X. Liu, J. Xiong, C. Yan, Designing safe electrolyte systems for a high-stability
lithium–sulfur battery, Adv. Energy Mater. (2018), 1702348, https://doi.org/
10.1002/aenm.201702348.
[14] S. Goriparti, E. Miele, F. De Angelis, E. Di Fabrizio, R. Proietti Zaccaria, C. Capiglia,
Review on recent progress of nanostructured anode materials for Li-ion batteries,
J. Power Sources 257 (2014) 421–443, https://doi.org/10.1016/j.
jpowsour.2013.11.103.
[15] S. Goutam, N. Omar, P. Van Den Bossche, J. Van Mierlo, Review of
Nanotechnology for Anode Materials in Batteries, Emerging Nanotechnologies in
Rechargeable Energy Storage Systems, Elsevier Inc, 2017, pp. 45–82, https://doi.
org/10.1016/B978-0-323-42977-1.00002-9.
[16] H.-J. Yen, H. Tsai, M. Zhou, E.F. Holby, S. Choudhury, A. Chen, L. Adamska,
S. Tretiak, T. Sanchez, S. Iyer, H. Zhang, L. Zhu, H. Lin, L. Dai, G. Wu, H.-L. Wang,
Structurally defined 3D nanographene assemblies via bottom-up chemical
synthesis for highly efficient lithium storage, Adv. Mater. 28 (46) (2016)
10250–10256, https://doi.org/10.1002/adma.201603613.
[17] H. Wang, J. Fu, C. Wang, J. Wang, A. Yang, C. Li, Q. Sun, Y. Cui, H. Li, A binder-
free high silicon content flexible anode for Li-ion batteries, Energy Environ. Sci. 13
(3) (2020) 848–858, https://doi.org/10.1039/C9EE02615K.
[18] B. Campbell, R. Ionescu, M. Tolchin, K. Ahmed, Z. Favors, K.N. Bozhilov, C.
S. Ozkan, M. Ozkan, Carbon-coated, diatomite-derived nanosilicon as a high rate
capable Li-ion battery anode, Sci. Rep. 6 (2016) 33050, https://doi.org/10.1038/
srep33050.
[19] M.H. Modarres, J.H.-W. Lim, C. George, M. De Volder, Evolution of reduced
graphene oxide–SnS2 hybrid nanoparticle electrodes in Li-ion batteries, J. Phys.
Chem. C 121 (24) (2017) 13018–13024, https://doi.org/10.1021/acs.
jpcc.7b02878.
[20] H. Wan, G. Peng, X. Yao, J. Yang, P. Cui, X. Xu, Cu2ZnSnS4/graphene
nanocomposites for ultrafast, long life all-solid-state lithium batteries using lithium
metal anode, Energy Storage Mater. 4 (2016) 59–65, https://doi.org/10.1016/j.
ensm.2016.02.004.
[21] Y. Yin, W. Liu, N. Huo, S. Yang, Synthesis of vesicle-like MgFe2O4/graphene 3D
network anode material with enhanced lithium storage performance, ACS Sustain.
Chem. Eng. 5 (1) (2017) 563–570, https://doi.org/10.1021/
acssuschemeng.6b01949.
[22] B. Wang, J.S. Chen, H.B. Wu, Z. Wang, X.W. Lou, Quasiemulsion-templated
formation of α-Fe2O3 hollow spheres with enhanced lithium storage properties,
J. Am. Chem. Soc. 133 (43) (2011) 17146–17148, https://doi.org/10.1021/
ja208346s.
[23] S. Fang, D. Bresser, S. Passerini, Transition metal oxide anodes for electrochemical
energy storage in lithium- and sodium-ion batteries, Adv. Energy Mater. 10 (1)
(2020), 1902485, https://doi.org/10.1002/aenm.201902485.
[24] W. Qi, J.G. Shapter, Q. Wu, T. Yin, G. Gao, D. Cui, Nanostructured anode materials
for lithium-ion batteries: principle, recent progress and future perspectives,
J. Mater. Chem. A 5 (37) (2017) 19521–19540, https://doi.org/10.1039/
C7TA05283A.
[25] X. Zhang, D. Wang, X. Qiu, Y. Ma, D. Kong, K. Müllen, X. Li, L. Zhi, Stable high-
capacity and high-rate silicon-based lithium battery anodes upon two-dimensional
covalent encapsulation, Nat. Commun. 11 (1) (2020) 3826, https://doi.org/
10.1038/s41467-020-17686-4.
[26] R. SenthilKumar, C. Nithya, S. Gopukumar, M. AnbuKulandainathan, Diamondoid-
structured Cu–dicarboxylate-based metal–organic frameworks as high-capacity
anodes for lithium-ion storage, Energy Technol. 2 (11) (2014) 921–927, https://
doi.org/10.1002/ente.201402076.
[27] H. Hu, X. Lou, C. Li, X. Hu, T. Li, Q. Chen, M. Shen, B. Hu, A thermally activated
manganese 1,4-benzenedicarboxylate metal organic framework with high anodic
capability for Li-ion batteries, New J. Chem. 40 (11) (2016) 9746–9752, https://
doi.org/10.1039/C6NJ02179D.
[28] F. Baskoro, H.Q. Wong, K.B. Labasan, C.-W. Cho, C.-W. Pao, P.-Y. Yang, C.-
C. Chang, C.-I. Chen, C.-C. Chueh, W. Nie, H. Tsai, H.-J. Yen, An efficient and
reversible battery anode electrode derived from a lead-based metal–organic
framework, Energy Fuels 35 (11) (2021) 9669–9682, https://doi.org/10.1021/acs.
energyfuels.1c00517.
[29] F. Baskoro, C.-M. Ngue, K.B. Labasan, H.Q. Wong, M.-K. Leung, H.-J. Yen, Dual-
ligand Zn-based metal–organic framework as reversible and stable anode material
for next generation lithium-ion batteries, Energy Technol. 9 (11) (2021), 2100212,
https://doi.org/10.1002/ente.202100212.
[30] M.E. Bhosale, S. Chae, J.M. Kim, J.-Y. Choi, Organic small molecules and polymers
as an electrode material for rechargeable lithium ion batteries, J. Mater. Chem. A 6
(41) (2018) 19885–19911, https://doi.org/10.1039/C8TA04906H.
[31] X. Han, C. Chang, L. Yuan, T. Sun, J. Sun, Aromatic carbonyl derivative polymers
as high-performance Li-ion storage materials, Adv. Mater. 19 (12) (2007)
1616–1621, https://doi.org/10.1002/adma.200602584.
[32] K.B. Labasan, H.-J. Lin, F. Baskoro, J.J.H. Togonon, H.Q. Wong, C.-W. Chang, S.
D. Arco, H.-J. Yen, Dicyanotriphenylamine-based polyimides as high-performance
electrodes for next generation organic lithium-ion batteries, ACS Appl. Mater.
Interfaces 13 (15) (2021) 17467–17477, https://doi.org/10.1021/
acsami.1c00065.
F. Baskoro et al.
[33] S.-H. Park, P.J. King, R. Tian, C.S. Boland, J. Coelho, C. Zhang, P. McBean,
N. McEvoy, M.P. Kremer, D. Daly, J.N. Coleman, V. Nicolosi, High areal capacity
battery electrodes enabled by segregated nanotube networks, Nat. Energy 4 (7)
(2019) 560–567, https://doi.org/10.1038/s41560-019-0398-y.
[34] R. Fang, K. Chen, L. Yin, Z. Sun, F. Li, H.-M. Cheng, The regulating role of carbon
nanotubes and graphene in lithium-ion and lithium–sulfur batteries, Adv. Mater.
31 (9) (2019), 1800863, https://doi.org/10.1002/adma.201800863.
[35] R. Raccichini, A. Varzi, S. Passerini, B. Scrosati, The role of graphene for
electrochemical energy storage, Nat. Mater. 14 (3) (2015) 271–279, https://doi.
org/10.1038/nmat4170.
[36] Y.H. Kwon, K. Minnici, J.J. Park, S.R. Lee, G. Zhang, E.S. Takeuchi, K.J. Takeuchi,
A.C. Marschilok, E. Reichmanis, SWNT Anchored with carboxylated polythiophene
“links” on high-capacity Li-ion battery anode materials, J. Am. Chem. Soc. 140 (17)
(2018) 5666–5669, https://doi.org/10.1021/jacs.8b00693.
[37] Z. Ju, X. Zhang, S.T. King, C.D. Quilty, Y. Zhu, K.J. Takeuchi, E.S. Takeuchi, D.
C. Bock, L. Wang, A.C. Marschilok, G. Yu, Unveiling the dimensionality effect of
conductive fillers in thick battery electrodes for high-energy storage systems, Appl.
Phys. Rev. 7 (4) (2020), 041405, https://doi.org/10.1063/5.0024123.
[38] L.-L. Lai, L.-Y. Wang, C.-H. Lee, Y.-C. Lin, K.-L. Cheng, Nanomaterials of triazine-
based dendrons: convergent synthesis and their physical studies, Org. Lett. 8 (8)
(2006) 1541–1544, https://doi.org/10.1021/ol0531076.
[39] L.-L. Lai, J.-W. Hsieh, K.-L. Cheng, S.-H. Liu, J.-J. Lee, H.-F. Hsu, A small change in
central linker has a profound effect in inducing columnar phases of triazine-based
unconventional dendrimers, Eur. J. Chem. 20 (17) (2014) 5160–5166, https://doi.
org/10.1002/chem.201303913.
[40] R. Deschenaux, B. Donnio, D. Guillon, Liquid-crystalline fullerodendrimers, New J.
Chem. 31 (7) (2007) 1064–1073, https://doi.org/10.1039/B617671M.
[41] M. Marcos, R. Martín-Rapún, A. Omenat, J.L. Serrano, Highly congested liquid
crystal structures: dendrimers, dendrons, dendronized and hyperbranched
polymers, Chem. Soc. Rev. 36 (12) (2007) 1889–1901, https://doi.org/10.1039/
B611123H.
[42] C.E. Chan-Thaw, A. Villa, L. Prati, A. Thomas, Triazine-Based Polymers as
Nanostructured Supports for the Liquid-Phase Oxidation of Alcohols, Eur. J. Chem.
17 (3) (2011) 1052–1057, https://doi.org/10.1002/chem.201000675.
[43] J. Zhu, J.L. Faria, J.L. Figueiredo, A. Thomas, Reaction mechanism of aerobic
oxidation of alcohols conducted on activated-carbon-supported cobalt oxide
catalysts, Eur. J. Chem. 17 (25) (2011) 7112–7117, https://doi.org/10.1002/
chem.201003025.
[44] S. Ren, M.J. Bojdys, R. Dawson, A. Laybourn, Y.Z. Khimyak, D.J. Adams, A.
I. Cooper, Porous, fluorescent, covalent triazine-based frameworks via room-
temperature and microwave-assisted synthesis, Adv. Mater. 24 (17) (2012)
2357–2361, https://doi.org/10.1002/adma.201200751.
[45] J. Lim, G.M. Pavan, O. Annunziata, E.E. Simanek, Experimental and computational
evidence for an inversion in guest capacity in high-generation triazine dendrimer
hosts, J. Am. Chem. Soc. 134 (4) (2012) 1942–1945, https://doi.org/10.1021/
ja210122z.
[46] J. Roeser, K. Kailasam, A. Thomas, Covalent triazine frameworks as heterogeneous
catalysts for the synthesis of cyclic and linear carbonates from carbon dioxide and
epoxides, ChemSusChem 5 (9) (2012) 1793–1799, https://doi.org/10.1002/
cssc.201200091.
[47] S. Hug, M.E. Tauchert, S. Li, U.E. Pachmayr, B.V. Lotsch, A functional triazine
framework based on N-heterocyclic building blocks, J. Mater. Chem. 22 (28)
(2012) 13956–13964, https://doi.org/10.1039/C2JM31248D.
[48] J. Lim, E.E. Simanek, Synthesis of water-soluble dendrimers based on melamine
bearing 16 paclitaxel groups, Org. Lett. 10 (2) (2008) 201–204, https://doi.org/
10.1021/ol7024907.
[49] J. Lim, M.A. Mintzer, L.M. Perez, E.E. Simanek, Synthesis of odd generation
triazine dendrimers using a divergent, macromonomer approach, Org. Lett. 12 (6)
(2010) 1148–1151, https://doi.org/10.1021/ol902669g.
[50] A. Grafe, D. Janietz, T. Frese, J.H. Wendorff, Star-shaped discotic oligomesogens
based on radial pentakisphenylethynylbenzene moieties, Chem. Mater. 17 (20)
(2005) 4979–4984, https://doi.org/10.1021/cm051042v.
[51] C.-H. Lee, M.-R. Tsai, Y.-T. Chang, L.-L. Lai, K.-L. Lu, K.-L. Cheng, Preparation of
unconventional dendrimers that contain rigid nh-triazine linkages and peripheral
tert-butyl moieties for CO2-selective adsorption, Eur. J. Chem. 19 (32) (2013)
10573–10579, https://doi.org/10.1002/chem.201202161.
[52] E. Abbasi, S.F. Aval, A. Akbarzadeh, M. Milani, H.T. Nasrabadi, S.W. Joo,
Y. Hanifehpour, K. Nejati-Koshki, R. Pashaei-Asl, Dendrimers: synthesis,
applications, and properties, Nanoscale Res. Lett. 9 (1) (2014) 247, https://doi.
org/10.1186/1556-276X-9-247.
[53] Z. Man, P. Li, D. Zhou, R. Zang, S. Wang, P. Li, S. Liu, X. Li, Y. Wu, X. Liang,
G. Wang, High-performance lithium–organic batteries by achieving 16 lithium
Electrochimica Acta 434 (2022) 141306
storage in poly(imine-anthraquinone), J. Mater. Chem. A 7 (5) (2019) 2368–2375,
https://doi.org/10.1039/C8TA11230D.
[54] S. Maiti, A. Pramanik, U. Manju, S. Mahanty, Reversible lithium storage in
manganese 1,3,5-benzenetricarboxylate metal–organic framework with high
capacity and rate performance, ACS Appl. Mater. Interfaces 7 (30) (2015)
16357–16363, https://doi.org/10.1021/acsami.5b03414.
[55] J. He, Y. Liao, Q. Hu, Z. Zeng, L. Yi, Y. Wang, H. Lu, M. Pan, Investigation of
polyimide as an anode material for lithium-ion battery and its thermal safety
behavior, Ionics 26 (7) (2020) 3343–3350, https://doi.org/10.1007/s11581-020-
03509-5.
[56] L. Hu, X.-M. Lin, J.-T. Mo, J. Lin, H.-L. Gan, X.-L. Yang, Y.-P. Cai, Lead-based
metal–organic framework with stable lithium anodic performance, Inorg. Chem. 56
(8) (2017) 4289–4295, https://doi.org/10.1021/acs.inorgchem.6b02663.
[57] P. Sengodu, C. Bongu, M. Perumal, M. Paramasivam, Easy synthesis of
microporous/mesoporous cobalt organic framework as binder less lithium-ion
battery electrode, J. Alloys Compd. 714 (2017) 603–609, https://doi.org/10.1016/
j.jallcom.2017.04.241.
[58] S. Renault, V.A. Oltean, C.M. Araujo, A. Grigoriev, K. Edström, D. Brandell,
Superlithiation of organic electrode materials: the case of dilithium
benzenedipropiolate, Chem. Mater. 28 (6) (2016) 1920–1926, https://doi.org/
10.1021/acs.chemmater.6b00267.
[59] S. Lee, G. Kwon, K. Ku, K. Yoon, S.-K. Jung, H.-D. Lim, K. Kang, Recent progress in
organic electrodes for Li and Na rechargeable batteries, Adv. Mater. 30 (42)
(2018), 1704682, https://doi.org/10.1002/adma.201704682.
[60] Y. Lu, Q. Zhang, L. Li, Z. Niu, J. Chen, Design strategies toward enhancing the
performance of organic electrode materials in metal-ion batteries, Chem 4 (12)
(2018) 2786–2813, https://doi.org/10.1016/j.chempr.2018.09.005.
[61] H. Yang, S. Liu, L. Cao, S. Jiang, H. Hou, Superlithiation of non-conductive
polyimide toward high-performance lithium-ion batteries, J. Mater. Chem. A 6 (42)
(2018) 21216–21224, https://doi.org/10.1039/C8TA05109G.
[62] B.T. McAllister, E. Grignon, T.B. Schon, S.Y. An, C.-H. Yim, Y. Abu-Lebdeh, D.
S. Seferos, High-rate activation of organic superlithiation anodes, ACS Appl.
Energy Mater. 4 (7) (2021) 6659–6666, https://doi.org/10.1021/acsaem.1c00714.
[63] Z. Zhang, Y. Zhou, P. Chen, S. Zeng, W. Nie, Y. Xu, Investigation of capacity
increase in Schiff-base networks as the organic anode for lithium-ion batteries, ACS
Appl. Energy Mater. 4 (11) (2021) 12882–12891, https://doi.org/10.1021/
acsaem.1c02569.
[64] J. Wang, J. Polleux, J. Lim, B. Dunn, Pseudocapacitive contributions to
electrochemical energy storage in TiO2 (Anatase) nanoparticles, J. Phys. Chem. C
111 (40) (2007) 14925–14931, https://doi.org/10.1021/jp074464w.
[65] F.-F. Li, J.-F. Gao, Z.-H. He, L.-B. Kong, Design and synthesis of cop/r-go
hierarchical architecture: dominated pseudocapacitance, fasted kinetics features,
and Li-ion capacitor applications, ACS Appl. Energy Mater. 3 (6) (2020)
5448–5461, https://doi.org/10.1021/acsaem.0c00440.
[66] V. Augustyn, J. Come, M.A. Lowe, J.W. Kim, P.-L. Taberna, S.H. Tolbert, H.
D. Abruña, P. Simon, B. Dunn, High-rate electrochemical energy storage through Li
+
intercalation pseudocapacitance, Nat. Mater. 12 (6) (2013) 518–522, https://doi.
org/10.1038/nmat3601.
[67] F. Yu, Z. Liu, R. Zhou, D. Tan, H. Wang, F. Wang, Pseudocapacitance contribution
in boron-doped graphite sheets for anion storage enables high-performance
sodium-ion capacitors, Mater. Horiz. 5 (3) (2018) 529–535, https://doi.org/
10.1039/C8MH00156A.
[68] T. Osaka, T. Momma, D. Mukoyama, H. Nara, Proposal of novel equivalent circuit
for electrochemical impedance analysis of commercially available lithium ion
battery, J. Power Sources 205 (2012) 483–486, https://doi.org/10.1016/j.
jpowsour.2012.01.070.
[69] A.J. Bard, L.R. Faulkner, Electrochemical Methods: Fundamentals and
Applications, 2nd Edition, Wiley Textbooks, 2000.
[70] C. Pastor-Fernández, K. Uddin, G.H. Chouchelamane, W.D. Widanage, J. Marco,
A comparison between electrochemical impedance spectroscopy and incremental
capacity-differential voltage as Li-ion diagnostic techniques to identify and
quantify the effects of degradation modes within battery management systems,
J. Power Sources 360 (2017) 301–318, https://doi.org/10.1016/j.
jpowsour.2017.03.042.
[71] S.J. An, J. Li, C. Daniel, D. Mohanty, S. Nagpure, D.L. Wood, The state of
understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI)
and its relationship to formation cycling, Carbon 105 (2016) 52–76, https://doi.
org/10.1016/j.carbon.2016.04.008.
[72] J. Billaud, F. Bouville, T. Magrini, C. Villevieille, A.R. Studart, Magnetically aligned
graphite electrodes for high-rate performance Li-ion batteries, Nat. Energy 1 (8)
(2016) 16097, https://doi.org/10.1038/nenergy.2016.97.