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

* Corresponding authors.
E-mail addresses: [email protected] (L.-L. Lai), [email protected] (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. Electrochimica Acta 434 (2022) 141306

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

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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 moieties [27]. The formation of a SEI layer at the electrode− electrolyte
potential at 2.42 V (inset Fig. 2a) could be ascribed to lithiation and interphase as suggested by the cathodic peak at roughly 0.54 V was
delithiation process of secondary amine. The reduction peak at 0.85 V on observed during the 1st cycle (shown in black) [54,55]. Nonetheless, the
the cathodic scan, and the oxidation peak at 1.02 V on the anodic scan CV curves exhibited remarkable cyclic stability without any change for
were attributed to the typical lithiation–delithiation process of C–
– N on each redox peak starting from the 2nd scan, demonstrating its structural
the triazine moieties in the DAP structure [53]. Meanwhile, the reduc­ integrity during the electrochemical process. Interestingly, the inclusion
tion and oxidation peaks at 0.02 V and 0.12 V, respectively, were of 1% CNT as a filler resulted in an enhanced capacitance on the CV
attributed to the typical Li+ insertion and de-insertion in other organic 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 V) and discharged stages (3.0 V), which possibly indicated the formation
efficient Li+ transport and intercalation. Furthermore, as shown in of an SEI layer on the DAP-based anode during the lithiation/delithia­
Fig. 2d, both pristine-DAP and DAP/CNT1% anode demonstrated an tion process. This also depicts that the Li+ insertion on the triazine and
excellent rate capability. The pristine-DAP anode delivered reversible piperazine played a major role in the battery performance.
capacities of 420, 396, 359, 325, and 275 mA h g− 1 as the current In addition, according to Faraday’s law, the theoretical capacity of
densities varied from 0.1, 0.5, 1.0, 2.0, and 5.0 A g− 1, respectively (black the polymer-based anode can be estimated using the equation, C = nF/
line). Meanwhile, the composite DAP/CNT1% exhibited reversible ca­ 3.6MW where C is the theoretical capacity, n is the accepted number of
pacities of 694, 537, 479, 421, and 348 mA h g− 1 as the current densities electrons, F is the Faraday constant (96485 C mol− 1), and Mw represents
varied from 0.1, 0.5, 1.0, 2.0, and 5.0 A g− 1, respectively (red line). The the molecular weight. As shown in Fig. 1a, if we assume that the lone
excellent rate capability was demonstrated as a high capacity of 425 and pair electron of nitrogen and the π electron could provide Li+ binding
694 mA h g− 1 was recovered for pristine-DAP and DAP/CNT1% anode, sites, the DAP (Mw = 6022 g mol− 1) can accommodate approximately
respectively, after the current density was reduced back to 0.1 A g− 1. 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
2.3. Li ion storage mechanism in DAP-based anode
mA h g− 1, which is consistent with our experimental result (Fig. 2c).
Therefore, based on our investigative analysis results, we proposed the
In order to verify the Li+ storage mechanism in the DAP-based anode,
lithiation/delithiation reaction of DAP-based anode as presented in
we employed the ex-situ FT-IR spectroscopy to evaluate the changes in
Scheme 1. In addition, this superlithiation stage has also been reported
the functional groups at different stages (Fig. 3). As depicted in Fig. 3,
in several organic-based electrodes such as polymer-based anodes
when the electrode was fully charged (0.02 V; blue line), the disap­
[58–63].
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

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

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.

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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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( )
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
negative pressure was applied to the container to enhance CNT filtra­
cycles, the DLi indicates that Li+ mobility in the DAP/CNT1% was one
tion. The deposited CNTs were re-integrated to become a film type. The
order magnitude faster (1.20 × 10− 12 cm2 s− 1) than that of pristine-DAP
CNT paper with the filtering paper was dried at 50◦ C for 24 h. There­
(8.07 × 10− 13 cm2 s− 1). This kinetical phenomenon is in good agreement
upon the CNT paper was carefully peeled from the filtering paper. The
with previous studies that the CNT as conductive filler could provide
size of CNT paper was 10 × 10 cm and the thickness was about 0.18 mm.
conductive network which significantly improve Li+ transport and
The areal weight was 0.64 mg cm− 2. The CNTs in a CNT paper are
reduce internal resistant [36,37]. Although, the DLi were relatively
preferentially oriented along the in-plane directions. Compared with
slower in both pristine-DAP and DAP/CNT1% after 200 cycles. This
their original forms of 3D irregular agglomerates, the CNT paper is flat,
phenomenon is possibly due to the formation of SEI that minimized Li+
flexible, self-standing and can be readily cut into size for application.
mobility [70,71].
Because of the continuous network of CNT integration, the CNT paper
In brief, the sweep rate CV and EIS studies revealed the importance of
becomes much more electrically-conductive than the original CNT
additional CNT filler in DAP-based anode. As shown in Fig. 4c and d, the
agglomerates.
sweep rate CV indicates additional 1% CNT tuned the charge storage
behavior of DAP-based anode by increasing capacitive contribution in
4.3. Characterization methods
the Li+ storage mechanism. Furthermore, the EIS study unleashed that
the Li+ diffusion coefficient dramatically increase one orders of
X-ray diffraction (XRD) measurements were measured on a Bruker
magnitude for DAP/CNT1% compare with the pristine-DAP electrode
D8 Advance X-ray Diffractometer at 40 kV and 40 mA using Cu Kα ra­
after 200 cycles (Table 1), implying an excellent Li+ transport during
diation (λ = 1.5406 Å). Fourier transform infrared spectroscopy (FT-IR)
charge/discharge cycling process thus result in significant increase Li+
were measured on a FT/IR 6600, JASCO International Co., Ltd. Scanning
storage capacity (Fig. 2c). This consistent with the previous study that
electron microscope (SEM) were performed using Field-Emission Scan­
revealed a better Li+ transport could significantly enhance battery per­
ning Electron Microscope (FESEM), Ultra Plus - Carl Zeiss. The nitrogen
formance [72]. We believe this phenomena are ascribed to highly
adsorption isotherms were measured at 77 K with an accelerated surface
conducive CNTs which allows rapid electron transfer and enhancing Li+
area and porosimetry system, Autochem II 2920 (Micromeritics, Nor­
transport, thus significantly improve the cycling performance of
cross, GA). Prior to the analysis, the sample was degassed at 50◦ C for 12
DAP-based anode.
h in a vacuum.
3. Conclusion
4.4. Coin cell preparation
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 To make the pristine-DAP anode, a homogeneous slurry mixture was
for Li-ion batteries. The results indicated that pristine-DAP as an anode made by mixing 60% conductive carbon (Super P®; >99% (metal basis);
material had a high specific capacity of 444 mA h g− 1 at 0.5 A g− 1, as UBIQ Technology Co., Ltd), 20% as-synthesized DAP, 20% poly(vinyli­
well as outstanding cycle stability, which might be attributed to its dene fluoride) (PVDF; UBIQ Technology Co., Ltd) as a binder, and N-
molecular structure containing triazine and piperazine units. The in­ methyl-2-pyrrolidone (NMP; Thermo Fisher Scientific) as solvent. The
clusion of carbon filler (CNTs) resulted in a considerable capacity in­ slurry was cast onto Cu foil and dried on a hot plate at 94 ℃ for 12 h,
crease of up to 656 mA h g− 1 at 0.5 A g− 1 after 200 cycles. Our study then for another 8 h at 80 ℃ in vacuo. A similar slurry process was used
suggests that the excellent electrochemical performance of the DAP/ to make the DAP/CNT1% anode, which consisted of 59% super-P, 20%
CNT composite is primarily due to the dendrimer’s effective structural as-synthesized DAP, 1% CNT paper, 20% PVDF binder, and NMP as
design, which includes an uneven number of carbon atoms on the cen­ solvent. For reference, a slurry consisting of 80% graphite (natural
tral linker, as well as the added conductive network provided by CNTs, graphite powder (GN-580L); UBIQ Technology Co., Ltd), 10% Super P,
resulting in high performance and long cycle life. 10% PVDF, and NMP as solvent was also prepared. The pristine-DAP,
DAP/CNT1%, and graphite electrodes were cut (12 mm in diameter)
4. Experimental 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.
4.1. Synthetic procedure of DAP dendrimer 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 DAP dendrimer was synthesized following previous procedure the as-prepared DAP-based anode as a working electrode, Li metal foil as
[39]. Briefly, 1,3-diaminopropane was allowed to react with one a counter/reference electrode, Celgard 2325 as a separator, and 40 μL of
equivalent of G3Cl dendron in dry tetrahydrofuran at 70 ℃ for 24 h. A 1 M LiPF6 in a 1:1 (v/v) ethylene carbonate/diethyl carbonate (EC/DEC;
further equivalent of G3Cl was added, followed by 5 equivalents of po­ UBIQ Technology Co., Ltd) as the electrolyte.
tassium carbonate, and the resulting mixture was reheated at 170 ℃ for
72 h in a sealed tube. The crude product was purified by chromatog­ 4.5. Electrochemical measurement
raphy and recrystallization to afford the pure triazine-based dendrimer
(referred to as DAP) with a yield of 69%. 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. Electrochimica Acta 434 (2022) 141306

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