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Dendrite-free lithium deposition on conventional

Cite this: DOI: 10.1039/d2ta01907h
graphite anode by growth of defective carbon-
nanotube for lithium-metal/ion hybrid batteries†
Gyuchan Yeo, a Jaekyung Sung,b Minhong Choi,a Namhyung Kim*c
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and Minseong Ko *a

Received 10th March 2022
Accepted 19th May 2022
DOI: 10.1039/d2ta01907h
rsc.li/materials-a
Conventional graphite faces theoretical capacity limitation, and conventional cells using graphite should
have a sufficient N/P ratio to avoid lithium plating on the surface of graphite. This lithium plating not only
causes severe cell degradation due to its poor reversibility but also causes critical safety issues by
penetrating the separator. In this study, we present defective carbon-nanotube-grown graphite that has
a high affinity for lithium deposition for electrochemical lithiation. These lithiophilic defective carbon
nanotubes can result in densely packed lithium deposition without any dendritic lithium plating, causing
poor reversibility and fatal safety issues. We observed that the dense lithium deposition on the defective-
carbon-nanotube grown graphite provides three times denser deposition and 13% improved initial
coulombic efficiency than dendritic lithium deposition on pristine graphite. As a result, in a full-cell
evaluation, the lithiophilic defective carbon growth graphite showed excellent cycle stability (83.7%) over
300 cycles even with a reverse designed N/P ratio (0.8), which can increase the energy density by
reducing the amount of anode and introducing lithium metal deposition on the anode surface.

deposited with a dendritic shape during the electrochemical

Introduction
The demand for high energy density batteries is rapidly
increasing owing to the commercialization of electric vehicles
and energy storage systems. Conventional lithium-ion batteries,
which use graphite as an anode material, have limited energy
density owing to the relatively low theoretical capacity of
graphite. For this reason, the development of high-capacity
anode materials is essential for achieving higher-energy-
density lithium-ion batteries. Recently, lithium metal has
been highlighted as a promising candidate for next-generation
anodes. Lithium metal has the lowest operating voltage (0 V vs.
Li/Li+) and high theoretical capacity (3860 mA h g
1), which are
advantageous for increasing energy density.1,2 However, there
are several fatal drawbacks resulting from severe volume vari-
ation and dendritic deposition of lithium metal limit its
commercial application.3–5 Metallic lithium tends to be
a
Metallurgical Engineering, Pukyoung National University, Busan 48547, Republic of
Korea. E-mail: msko876@pknu.ac.kr
b
Department of Nuclear Science and Engineering, Massachusetts Institute of
Technology, Cambridge, MA, USA
c
School of Energy and Chemical Engineering Green Energy Materials Development
Center, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919,
Republic of Korea. E-mail: namh.kim91@gmail.com
† Electronic supplementary information (ESI) available: PSA, BET, FE-SEM,
electrode thickness change aer lithiation and lithium plating, independent
capacity and ICE of graphite and deposited lithium, additional electrochemical
performances. See https://doi.org/10.1039/d2ta01907h
charging process, and this dendritic lithium growth can lead to
safety issues by penetrating the separator and causing a short
circuit. In addition, lithium deposition normally has a porous
and non-uniform structure by repeated deposition and strip-
ping processes, resulting in the acceleration of side reactions
between the electrode and electrolyte with the accumulation of
unstable solid electrolyte interphase (SEI) layers.6,7 Further-
more, heterogeneous stripping of lithium metal generates
“dead lithium”,8,9 which results in the loss of lithium in the
enclosed battery system. Acceleration of side reactions and the
formation of dead lithium leads to low coulombic efficiency
(CE) and poor life span of lithium metal batteries.10,11 Hence,
a strategy to enhance the CE and life span by suppressing
lithium dendrites is essential for the commercialization of
lithium metal.
Various strategies and experiments have been conducted to
control the characteristics of lithium metal deposition. First,
the coating of the articial layer was introduced onto the
surface of the lithium metal.12,13 Articial layers such as poly-
mers or carbonaceous materials induce the even deposition of
lithium metal with improved reversibility of lithium. Although
these articial coating layers have improved the overall elec-
trochemical reversibility of lithium metal batteries, there are
still several challenges for practical applications such as
extremely restricted and costly manufacturing processes owing
to the use of metallic lithium. Studies on the synthesis of
composites with lithiophilic noble metals have been reported

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Fig. 1 Schematic of the anode electrode with additional lithium metal deposition. (a) Top view and (b) cross-sectional image.
and have showed better performance by minimizing the lithium
nucleation overpotential.14–17 Despite their excellent improve-
ments, employing these noble metals is a critical cost issue. To
minimize the volume variation of the lithium metal anode, 3D
structured host materials have been suggested to have sufficient
room to accommodate lithium deposition without a large
volume change.18,19 These 3D hosts with high surface areas
effectively mitigated the volume variation due to their high
electrochemically active surface area. However, these 3D struc-
tures can occupy a large portion of the volume in the cell
conguration, leading to a lower volumetric energy density.
To address these challenges of lithium metal anodes by
considering practical factors, Dahn et al. recently suggested
a pioneering work on hybrid lithium metal anodes with
conventional graphite.20 In the study, excessive lithium was
electrochemically deposited on the surface of commercial
graphite during the charging process in a full-cell system by its
reverse designed negative to positive electrode capacity ratio (N/
P ratio). With the assistance of a customized electrolyte,
a homogeneous and densely deposited lithium layer was
formed on the graphite surface with a good CE. Moreover, the
plated lithium remained and worked without dead lithium
formation even aer long-term cycling. They found that, the
volumetric energy density of the hybrid electrode cells could be
20% higher than that of conventional graphite cells. The
combination of lithium metal with conventional graphite has
various advantages in overcoming both the capacity limitation
of graphite and the practical obstacles of a lithium metal anode.
However, despite the successful improvement in battery
performance, several challenges remain, such as the excessive
use of uoroethylene carbonate (FEC), which can cause
hydrogen uoride generation and following degradation of
battery performance.21,22
In this study, we synthesized a defective-carbon nanotube
(dCNT)-grown graphite (dCNT-G) composite material by simple
chemical vapor deposition (CVD) using hydrogen (H2) and
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ethylene (C2H4) gas. Commercial graphite was coated with
nickel hydroxide via a reux method, and the obtained sample
was consecutively annealed in a tube furnace with H2 and C2H4
gas ows, respectively. During the H2 ow, nickel hydroxide on
the surface of graphite was reduced and converted into metallic
nickel nanoparticles, which could act as a catalyst for the
growth of carbon nanotubes by reacting with C2H4 gas. The
CNTs grown on the nickel nanoparticles have a disordered
defective structure because of the randomly oriented catalytic
surface of the nickel particles. These dCNTs have good lith-
iophilic characteristics because of their defective structures
with highly reactive sites.23,24 Owing to this lithiophilic defective
site, the dCNT can effectively accommodate and guide the
plated Li ions in a dense and dendrite-free metal deposition
layer, as shown in Fig. 1. Consequently, in an excessive lith-
iation test in a half-cell using a conventional electrolyte, the
dCNT-G showed a dense and dendrite-free Li deposition layer
on the surface of the dCNT-G electrode and provided a relatively
stable Li deposition/stripping for repeated cycles compared to
pristine graphite. In addition, we also conducted a full-cell
evaluation even with a reverse-designed N/P ratio (0.8). This
reversed N/P ratio design can increase both the volumetric and
gravimetric energy densities of the cell by reducing the use of
the anode while retaining its cell capacity. In the full-cell
conguration, dCNT-G exhibited excellent cycle stability of
83.5% aer 300 cycles with a high average CE. As a result, dCNT-
G successfully increased the energy density by utilizing the
plated Li on the dCNT-G electrode as well as accommodating
the excessive metallic Li on the surface of the dCNT-G electrode
without any dendrite formation.
Experimental
Synthesis of dCNT-G
50 g of G (S360, BTR) and 5 g of nickel(II) nitrate hexahydrate
(Ni(NO3)2$6H2O > 99.999%, Sigma-Aldrich) were dissolved in
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methyl alcohol (CH3OH > 99.5%, Samchun) to perform reux
process. The reux process was carried out at 80  C for 30 min in
atmospheric air to disperse Ni precursor on G. To induce the
reduction and penetration of Ni, graphite with the Ni precursor
was performed at 700  C for 3 h under H2 (99.999%, KOSEM)
atmosphere (1000 sccm). The growth of dCNTs was followed
continuously in the same furnace with argon balanced ethylene
gas (9.99 mol% C2H4, KOSEM) ow at 930  C for 10 min (1000
sccm).
Material characterization
The structure of the samples was analyzed using eld-emission
scanning electron microscopy (FE-SEM, JSM-7401F, JEOL).
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Further analysis was carried out using HR-TEM (JEM-2100F,
JEOL) and a cross-sectional view of the electrode was per-
formed using a dual-beam FIB (Helios 450 HP, FEI). To measure
the particle size of the samples, PSA (Microtac S3500, Microtac)
was used and surface area was measured with a one-point BET
(HM model-1200, Macsorb).
Electrochemical characterization
The working electrode was prepared by mixing the active
material (G, dCNT-G) with a conductive agent (Super P, Timcal),
sodium carboxymethylcellulose, and styrene butadiene rubber
as the binding material. The mass ratio was xed at 95 : 1 : 2 : 2
and homogenously mixed and cast on a Cu current collector.
The mixed slurry was loaded up to 10.3 mg cm
2 and the elec-
trodes were dried at 80  C. Dried electrodes were calendared to
achieve 1.6 mg cm
3 using a roll press. The fabricated
Fig. 2 dCNT-G preparation process (a) scheme of the synthesis process of dCNT-G. Scanning electron microscopy images of (b) Graphite and
(c) dCNT-G. (d) HR-TEM image of dCNT grown at the surface of dCNT-G.
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electrodes were dried under vacuum at 120  C for 12 h. dCNT-G/
G electrode was fabricated by casting dCNT-G slurry above dried
G electrode and dried under vacuum at 120  C for 12 h. For the
fabrication of the cathode electrode, a slurry composed of NCM
622 (Cosmo AM&T CO.), carbon black, and polyvinylidene
uoride binder in a mass ratio of 94 : 3 : 3 was cast on an Al
current collector. A mass of 27 mg cm
2 was loaded and
calendared to achieve 3.6 mg cm
3 of electrode density. The
electrolyte used was 1.3 M LiPF6 in a mixture of ethylene
carbonate/ethyl methyl carbonate/diethyl carbonate (3 : 5 : 2, by
volume) with 10% FEC, 0.2% lithium tetrauoroborate, 0.5%
vinylene carbonate, and 1% propane sultone. The coin cell was
assembled using CR2032 and a separator (2320, Wellcos) in an
argon-lled glove box. Lithium metal (>99%, HONJO METAL
CO., 1 mm) was used as the counter electrode for the half-cell,
and NCM 622 was used as the counter electrode for the full-
cell test. The lithiation process of the half-cell test was
composed of a graphite lithiation process (constant current
(CC, 0.1C) mode with a 0.005 V cut-off voltage and constant
voltage (CV, 0.005 V) mode with 1/100C cut-off current), fol-
lowed by an additional lithium plating process (CC mode (0.1C)
with a xed capacity cut-off condition). The delithiation process
was carried in CC mode (0.1C) with a 1.5 V cut-off voltage.
Lithium cycling tests at half-cells were performed with CC mode
(0.1C) lithiation and delithiation with a xed capacity cut-off
condition.
Full cell conguration was performed with an N/P ratio of 0.8
and in a voltage range of 2.5 and 4.3 V at 0.1C for the initial
formation cycle. The rest of the cycle tests were carried in the
voltage range from 3.0 V and 4.3 V at a 0.3C rate. All cell tests
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were conducted using a battery cycler (WBCS3000Le32/
Wonatech) at 25  C.
Results and discussion
dCNT-G was prepared by the reux method and a series of CVD
processes via hydrogen reduction and growth of dCNTs, as
shown in Fig. 2a. First, nickel hydroxide was homogeneously
dispersed on the surface of conventional graphite (G) by the
reux process. The sample was then placed in a tube furnace for
hydrogen reduction and growth of dCNTs. By calcination at
700  C in H2 atmosphere, Ni precursors were reduced to Ni for
use as a catalyst for dCNT growth.25–27 The growth of the dCNTs
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These dCNTs exhibit a unique structure with additional
defective sites based on the low temperature and partial pres-
sure of CVD process.30 Further particle size analysis (PSA) and
Brunauer–Emmett–Teller (BET) measurements were carried out
to identify the particle size and surface area of the dCNT-G
(Fig. S1†). Although the particle size of two materials was
similar, the surface area of the dCNT-G (27.49 m2 g
1) was 13
times higher than that of G (2.06 m2 g
1) because of the intro-
duction of dCNTs. The defective structure of dCNT-G was
conrmed by Raman spectra (Fig. S2†). dCNT-G showed higher
D peak (1350 cm
1) and D/G ratio (0.31) compared to G (0.17)
which indicates increase of defective structure at graphitic
materials.31 The defective structure and high surface area of the

was followed continuously for thermal reduction by maintain-
ing the temperature at 700  C and converting the inner atmo-
sphere by owing ethylene gas (C2H4). Owing to the catalytic
effect of the Ni sites and dissociated C2H4 gas, growth of the
dCNTs occurs between the Ni particles and graphite.28,29 Scan-
ning electron microscopy (SEM) images of G (Fig. 2b) and dCNT-
G (Fig. 2c) conrm the homogeneous growth of the dCNTs at
the surface of the G.
dCNT could provide favorable conditions for lithium deposition
(lithiophilic), and dCNT-G is expected to induce homogeneous
and compact lithium deposition while securing improved
stability. Furthermore, the structure of the dCNTs was observed
using high resolution transmission electron microscope (HR-
TEM) in Fig. 2d.
To investigate the effect of dCNTs on lithium deposition, the
electrochemical performances of G and dCNT-G were examined

Fig. 3 Electrochemical performance of G and dCNT-G in half-cell configuration. (a) Voltage profiles of G and dCNT-G at initial cycle with the
additional lithium deposition process. (b) Potentials at the beginning and after 40 mA h g
1 lithium plating of G and dCNT-G. (c) Voltage profiles
for 50 cycles of plated lithium with 100 mA h g
1 at G and dCNT-G. Voltage profiles at the discharge of (d) 1st, (e) 30th, (f) 50th cycle of G and
dCNT-G. (g) Average discharge voltages during 40 cycles of cycled lithium with 100 mA h g
1 at G and dCNT-G. (h) Delithiation capacities
originated from lithium and graphite (G, dCNT-G) for 50 cycles.

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with a 2032-coin cell using a conventional carbonate electrolyte
(ethylene carbonate : ethyl methyl carbonate : diethyl carbonate
¼ 3 : 5 : 2). The half-cell was assembled with a G or dCNT-G
electrode as the working electrode and lithium metal as the
counter electrode. G and dCNT-G were fully lithiated at 0.1C-
rate (33 mA g
1). Subsequently, an additional lithium deposi-
tion process was performed at 0.1C for additional lithium
deposition. As shown in Fig. 3a, the voltage prole shows two
different voltage plateaus, which correspond to the lithiation of
graphite and lithium deposition. Since the additional lithium
was deposited above graphite, delithiation process presented
two different voltage plateaus of graphite and lithium metal,
and the enlarged voltage prole is shown in Fig. S3.† Based on
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Fig. S3,† we separately derived the performance along the
graphite and lithium regions, and the results are listed in Table
S1.† dCNT-G showed an approximately 5% lower initial CE in
the graphite region due to the high surface area of the dCNTs;
however, the initial CE in the lithium region was 13% higher
than that of G. As a result, despite the extremely high surface
area of the dCNT-G, the initial CEs for the overall reactions
showed similar results for the G (89%) and dCNT-G (90%)
electrodes. To investigate the inuence of the grown dCNTs at
nucleation of lithium metal, an additional lithium plating
process was carried out at charging rates of 0.1, 1, 3, and 5C
(Fig. S4†). Fig. 3b displays the initial voltages and voltages aer
40 mA h g
1 of lithium plating at diverse C-rates. The initial
voltages are much lower based on the impact of the over-
potential. This overpotential demonstrates the resistance to the
initial lithium deposition at the surface of the anode electrode.
For dCNT-G, the difference between these voltages was slight
even with an increase in the C-rate, and the highest difference
was 0.1404 V at 5C. However, G showed a voltage difference of
Fig. 4 SEM images of (a) the top (b) and the cross-section of G electrode and (c) the top (d) and the cross-section of dCNT-G electrode after
extra lithium plating of 140 mA h g
1.
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0.2358 V at 5C, which was approximately 1.5 times higher
voltage difference compared to that of dCNT-G. Furthermore,
the average voltage difference of G from 1C to 5C was 0.2276 V,
and that of the dCNT-G was lower than in G at all diverse
charging rates (0.1, 1, 3, and 5C); these results indicate the
overpotential relived by the presence of lithophilic dCNTs.
These results show that dCNT-G effectively relieved the resis-
tance to Li deposition while showing a lower overpotential for
the nucleation of lithium.
Furthermore, half-cell cycling tests with additional depos-
ited lithium were performed to estimate the stability of the
deposited lithium layer. A xed amount of lithium
(140 mA h g
1) was initially deposited at both the G and dCNT-G
electrodes aer lithiation of graphite by an additional lithium
plating process (Fig. S5†). Aer the lithium stripping process,
cycling tests were performed within 100 mA h g
1 to conrm the
reversibility of lithium deposition on G and dCNT-G. Fig. 3c and
S6† show the voltage prole of lithium plating/stripping for 50
cycles at the G and dCNT-G electrodes. The voltage proles for
the rst cycle of G and dCNT-G demonstrate only one plateau,
which corresponds to the lithium stripping/plating reaction, as
shown in Fig. 3d. However, with the number of cycles, contin-
uous lithium loss induced graphite to participate in the
discharge process. At the 30th cycle, as shown in Fig. 3e and
a second plateau was observed aer the lithium stripping
voltage during the discharge process, which indicated the
delithiation of graphite. Since lithiophilic dCNTs were grown at
the surface of dCNT-G, the plating/stripping reaction of lithium
metal showed improved reversibility. As a result, the discharge
capacity originating from lithium was much higher at dCNT-G
(92 mA h g
1) than that of G (38 mA h g
1). Lithium loss was
accumulated by repeated cycles of lithium, and the occupation
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at delithiation capacity of lithium decreased with the following
cycles, as shown in Fig. 3f. These results come along with the
results displayed at Fig. 3g and h, which show the average
delithiation voltage and individual delithiation capacity of
lithium and graphite materials (G, dCNT-G). In Fig. 3g and
a sharp increase in the average voltage is observed at G aer the
26th cycle because graphite starts to participate in delithiation
capacity, as shown in Fig. 3h. In the case of dCNT-G, the amount
of capacity compensated from graphite was relatively low due to
less amount of lithium loss while cycling, displayed lower
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increasement of average voltage. Aer 40 cycles, the delithiation
capacity of lithium metal seemed to be xed with only small
variations; nally, G and dCNT-G showed a stabilized remaining
lithium capacity of 16 mA h g
1 and 48 mA h g
1 at the 50th
cycle. In cycling tests with increased cycling capacity within
200 mA h g
1, dCNT-G retained 86 mA h g
1 of stabilized
lithium, as shown in Fig. S7 and S8.† The overall electro-
chemical results demonstrated a favorable effect of dCNTs
during lithium deposition. In short, lithium layer on the dCNT-
G showed improved stability and reversibility compared to

Fig. 5 Electrochemical performance of G, dCNT-G, and dCNT-G/G electrode in full-cell configuration. (a) Scheme of concept for dCNT-G/G
electrode (b) cross-sectional SEM image of G and d CNT-G/G electrode. (c) Initial formation cycle voltage profile of G, dCNT-G, and dCNT-G/G
(0.1C). (d) The discharge capacity of G, dCNT-G, and dCNT-G/G at early 40 cycles. (e) CE and discharge capacity of G, dCNT-G, and dCNT-G/G
for 300 cycles (0.3C). Inset graphs are CE of G, dCNT-G, and dCNT-G/G at early 10 cycles.

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Paper
lithium layer on the G owing to the relief of resistance and
stable lithium deposition by lithiophilicity and high surface
area.
To conrm the morphology of the deposited lithium, SEM
analysis was carried out at the G and dCNT-G electrodes aer
charging and additional lithium plating with a xed capacity
(140 mA h g
1). Despite the xed capacity of additional lithium
deposition, the morphology of the deposited lithium layer was
quite different between the deposited lithium above G and
dCNT-G, as shown in Fig. 4. In case of the G, a dendritic and
clumsy lithium layer was formed. This dendritic lithium layer
has a higher surface area and favorable to form the dead
lithium, thereby it reduced the reversibility of the deposited
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lithium.32,33 Therefore, we could infer that the poor half-cell
properties of the G (Fig. 3) are originated from the needle-
shaped deposition of lithium. In contrast, the dense and non-
dendritic deposition of lithium was induced by the dCNTs
that existed on the surface of the dCNT-G. Even when the same
amount of lithium the G, as shown in Fig. 4b and d. Further-
more, the dCNT-G electrode showed a lower thickness change
with 470 mA h g
1 lithium plating compared to the
140 mA h g
1 lithium plating result of the G electrode (Fig. S9
and Table S2†). The former half-cell congurations and SEM
analysis exhibits that the morphology of the deposited lithium
affects the electrochemical performance. The dendritic depo-
sition of lithium easily forms dead lithium, which induces extra
lithium loss and degradation of the CE. The high surface
property of dendritic morphology also accelerates capacity
degradation by the formation of excessive SEI and electrolyte
consumption. In contrast, dCNT-G led the compact deposition
of lithium compared to dendritic deposition on the G and
marked higher reversibility and stability of the deposited
lithium.
To investigate the potential for the realistic application of
dCNT-G, a full cell test was performed with LiNi0.6Co0.2Mn0.2O2
(NCM622) as the cathode material. As mentioned, excess
capacity of the anode electrode (N/P ratio > 1) is still required to
prevent lithium deposition, which has poor morphology and
results in degradation of cell performance.34 When the anode
material could utilize the surface-deposited lithium as a revers-
ible capacity source, a higher energy density could be attained
with a lower loading level of the anode electrode, while the
capacity of the cathode was xed (N/P < 1).
Since dCNT-G showed improved reversibility of deposited
lithium, we expected that dCNT-G could overcome the limitations
of the N/P ratio by utilizing surface-deposited lithium metal.
However, even when dCNT-G induced a stable lithium layer, the
initial CE of dCNT-G without considering lithium deposition was
lower than that of G (Table S1†). Moreover, the deposition of
lithium is predominantly originated at the surface of the electrode
(Fig. 5a). Based on these factors, we designed a double-layer elec-
trode (dCNT-G/G) with a basal G layer and a thin dCNT-G layer at
the top, as shown in Fig. 5b and S10.† The full cell was designed
with a reversed N/P ratio (0.8), which has a larger capacity of the
cathode electrode compared to the anode electrode. The rst-cycle
voltage proles of G, dCNT-G, and dCNT-G/G are shown in Fig. 5c.
dCNT-G showed a 4% lower initial CE (82%) compared to G (86%)
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owing to the increased side reaction between the electrode and
electrolyte by the dCNTs. In addition, the initial CE of G was lower
than that of the half-cell test and common graphite materials
because of the poor CE of the additionally deposited lithium metal.
In the case of dCNT-G/G, the initial CE was the highest among the
three electrodes because the optimized amount of dCNT-G and the
compact dCNT-G layer successfully introduced stable deposition of
the lithium metal. Along with the previous half-cell conguration,
cycle retentions were dominantly affected by early cycles, where the
loss of lithium appeared with surface-deposited lithium. The
relationship between loss of lithium metal and the capacity decay
at early cycles could be proved by the full cell conguration that
successfully remained discharge capacity when additional lithium
was deposited before full cell assembly (Fig. S11†). In addition, the
full cell conguration with an additional lithium-deposited elec-
trode showed improved capacity retention due to the extra lithium.
Fig. 5d displays the discharge capacity of three electrodes at early
40 cycles, and dCNT-G/G showed the highest capacity retention of
89%. The other electrodes exhibited steep degradation of
discharge capacity which induces loss of lithium. As a result, the
capacity retention of the G electrode was 70% at the 300th cycle as
shown in Fig. 5e. The remained capacity was even lower than the
capacity of graphite without lithium deposition. This result
represents the limitation of conventional graphite at the reverse
designed N/P ratio which provides additional lithium source. In
contrast, the dCNT-G electrode exhibited 77% of capacity retention
at the 300th cycle, which was affected by the lower lithium capacity
loss at the early cycles with a stable plate-shaped lithium layer.
Based on the stable lithium layer induced by the dCNTs, the
capacity retention was improved by 7% compared to that of G.
However, the maintained discharge capacity at the 300th cycle was
still lower than the originally designed capacity ratio of graphite
(0.8) because of the relatively high side reaction of dCNT-G. With
the optimized quantity of dCNT-G, the d-CNTG/G electrode
showed capacity retention of 84% at the 300th cycle, which was
13.5% higher than that of the G electrode. It is worthwhile
mentioning that the remaining capacity was higher than the
reversed N/P ratio (0.8). In the case of G and dCNT-G, further
capacity loss was induced which exceeds additionally supplied
capacity by reversed N/P ratio due to extremely high amount of
lithium loss. In contrast, dCNT-G/G showed extra lithium
remaining aer 300 cycles, while using it as a reversible capacity
source for a full cell system. To summarize, the superior perfor-
mance of the dCNT-G could overcome the restricted N/P ratio and
limited capacity of G by effective utilization of surface-deposited
lithium as an extra capacity source.
Conclusions
In this work, we introduced dCNTs to commercial graphite by
simple synthetic processes and successfully induced stable
excess lithium deposition at the surface of the graphite elec-
trode owing to the high surface area and lithiophilic behaviour
of the defects in dCNTs. We found that dCNT-G led to densely
deposited lithium plating without dendritic Li formation, while
G showed dendritic growth of deposited lithium. Owing to the
dendritic morphology of the deposited lithium at G, the
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Journal of Materials Chemistry A
deposited lithium showed poor reversibility and severe loss of
active lithium during repeated cycles. Meanwhile, in the case of
dCNT-G, densely deposited lithium exhibited improved revers-
ibility and about two times higher amount of active lithium
metal even aer 50 cycles compared to that of G. To conrm the
possibility of using the dCNT-G for utilizing extra lithium as
a reversible capacity source, a full-cell test was performed with
a reverse designed N/P ratio (0.8). The overall electrochemical
cell test was conducted using a conventional carbonate elec-
trolyte and commercial electrode conditions. The dCNT-G/G
electrode showed an initial CE of 87.0% and the highest
capacity retention of 83.5% at the 300th cycle. It is noticeable
that the maintained capacity of dCNT-G/G was higher than that
Published on 05 June 2022. Downloaded by KIER on 6/16/2022 8:23:34 AM.
of graphite. This high capacity indicated that the deposited
lithium on dCNT-G remained electrochemically active even
aer 300 cycles. Based on the ndings of this study, we propose
that the dCNT-G has the potential to utilize lithium metal with
G as a Li–graphite hybrid anode while overcoming both the
limited capacity of graphite and poor reversibility of lithium
metal in the carbonate electrolyte.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was partly supported by ITECH R&D program of
MOTIE/KETI (project No. 20007171)and the National Research
Foundation of Korea (NRF) grant funded by the Korea govern-
ment (MSIT) (No. 2021R1A2C1095408).
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