Research Article

Cite This: ACS Appl. Mater. Interfaces 2018, 10, 41380−41388 www.acsami.org

Marriage of an Ether-Based Electrolyte with Hard Carbon Anodes

Creates Superior Sodium-Ion Batteries with High Mass Loading
Yongwu He,† Panxing Bai,† Shuyan Gao,*,‡ and Yunhua Xu*,†,§
†
School of Materials Science and Engineering, Key Laboratory of Advanced Ceramics and Machining Technology (Ministry of
Education), Tianjin Key Laboratory of Composite and Functional Materials, and Tianjin Key Laboratory of Molecular
Optoelectronic Science, Tianjin University, Tianjin 300072, China
‡
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China
§
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China
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*
S Supporting Information

ABSTRACT: Inferior rate performance, insufficient cycle life, and low mass loading have
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restricted the practical application of hard carbon (HC) anodes in sodium-ion batteries
(NIBs). Here, a compatible strategy is developed by matching HC anodes with an ether-
based electrolyte. Systematical investigation reveals that good compatibility of the
electrode−electrolyte systems forms thinner but a more sustainable solid-electrolyte
interphase and delivers a higher ionic conductivity and Na+ ion diffusion coefficient than
the commonly used ester-based electrolytes. Therefore, an excellent electrochemical
performance is demonstrated with a long cycle life (∼196 mA h/g and 90% capacity
retention after 2000 cycles at 1 A/g), a super rate capability (∼51% capacity retention at
10 A/g) at a mass loading of 1.5 mg/cm2, and a high initial Coulombic efficiency of
85.9%. More importantly, a high reversible areal capacity of 4.3 mA h/cm2 can be
achieved at an ultrahigh mass loading of 17 mg/cm2, superior to all reported HC anodes.
Our findings not only shed light on the design of high-performance battery systems but
also promise a commercial transformation from the lab test to mass production of NIBs.
KEYWORDS: sodium-ion battery, hard carbon anode, ether-based electrolyte, solid-electrolyte interphase, interfacial kinetics,
high mass-loading anode

■ INTRODUCTION
Lithium-ion batteries (LIBs), as the most successful energy
storage system, have been widely deployed in portable
electronic devices and electric vehicles because of their long
cycle life and high energy density.1 With the growing demand
for LIBs, the limited reserves and uneven geographical
distribution of lithium in the Earth’s crust will certainly trigger
resources and cost issues and therein impede their large-scale
applications in the future. With the advantages of abundance
and facile accessibility of sodium resources and the similar
intercalation chemistry between sodium and lithium, sodium-
ion batteries (NIBs) have recently attracted increasing
attention as a promising candidate for large-scale stationary
energy storage.2,3
In contrast to the considerable progress made for cathode
materials in NIBs, the exploration of anode materials remains a
great challenge. Graphite, the standard anode material in
commercial LIBs, does not function well for NIBs due to the
larger radius of Na+ ions (1.02 Å) compared to that of Li+ ions
(0.76 Å) and thermodynamic instability of sodium−graphite
intercalation compounds, giving a low specific capacity either
in ester-based electrolytes or in ether-based electrolytes.4,5
Unremitting efforts have been devoted to prescreening anode
materials for NIBs, such as carbonaceous materials (mainly
amorphous carbons),6−11 alloy-based materials (Sb, P, Sn, and
Bi), 12−18 oxides, 19,20 sulfides, 21−23 and organic com-
pounds.24,25 Carbonaceous materials hold good resiliency
and conductivity, which provide a robust mechanical support
to alleviate the volume changes caused by Na ion insertion and
ensures a good electronic conductivity, making them the ideal
host materials to NIBs. Among them, hard carbon (HC)
anodes show the most promising performance with a capacity
of 250−400 mA h/g and a low voltage plateau of ∼0.1 V.4,26,27
Particularly, HC materials can be prepared from abundant and
renewable biomass resources, which meets the low-cost
requirement for mass manufacture.28−37
However, the HC anodes are often subjected to a poor rate
performance where most failed at a current density of 1 A/g or
lower and insufficient lifespan, making them less competitive
for practical applications. Recently, the tailored electrolytes and
solid-electrolyte interphase (SEI) layers have been employed
to improve the performance of carbon anode materials in
NIBs.38−40 Yang’ group reported that the optimized SEI layers
formed in an ether-based electrolyte can be conducive to
Received: September 3, 2018
Accepted: November 7, 2018
Published: November 7, 2018

© 2018 American Chemical Society 41380 DOI: 10.1021/acsami.8b15274

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Figure 1. Structure characterization: (a) SEM and (b) HRTEM images, (c) XRD pattern, (d) Raman spectrum and high-resolution XPS spectra of
(e) C 1s, (f) O 1s, and (g) N 1s of the HC.
achieve superb sodium storage performance for reduced
graphene oxide anodes.38 Similarly, Zhou’s group employed
an ether-based electrolyte to reduce the electrochemical
polarization and modify the SEI layers, which enhanced the
rate capability of HC anodes, but still a poor cycling stability.39
Very recently, we reported a new strategy to stabilize the HC
anodes in an ether-based electrolyte by preengineering a
“foreign SEI” from an ester-based electrolyte and demonstrated
a significantly improved electrochemical performance with no
detectable capacity loss over 1000 cycles.40 However, sustained
efforts are still needed to produce better HC anodes that
simultaneously possess high rate capability and long-term
cycling stability.
Besides the good electrochemical performance of the HC
anodes, high mass loading is another critical parameter for
practical applications. So far, the mass loading of HC anodes
reported in the literature is too low, mostly around 1.0 mg/
cm2, delivering a specific areal capacity of 0.3 mA h/cm2 (given
the gravimetric specific capacity of the HC anodes is 300 mA
h/g).27,35,41 Recently, improved mass loadings have been
achieved in some carbon anodes for NIBs, reaching 4 mg/cm2
with an areal specific capacity of 1.2 mA h/cm2.28,42 However,
there still exists a big gap between the lab test results and the
commercial requirement (∼3.7 mA h/cm2 for graphite anodes
in commercial LIBs).43,44
In this work, an ether-based electrolyte was applied to
circumvent the challenges that the HC anodes are facing in
NIBs. The ether-based electrolyte performs a better wettability,
creates a thinner but a more sustainable SEI, and delivers a
higher ionic conductivity and Na+ ion diffusion coefficient in
HC compared with the widely used ester-based electrolytes
and thus enabling an excellent electrochemical performance of
HC anodes in terms of high initial Coulombic efficiency (ICE)
of 85.9%, long cycle life (retaining 196 mA h/g after 2000
cycles at 1 A/g), high rate capability (delivering 139 mA h/g at
a very high rate of 10 A/g), and above all, high mass loading
(reaching 17 mg/cm2 with a high specific areal capacity of 4.3
mA h/cm2). The specific areal capacity is not only much better
than those HC anodes reported in the literature but also
comparable with those commercial graphite anodes in
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LIBs.27,35,41,43,44 The compatibility between the ether-based
electrolyte and HC anodes contributes to the superior kinetics
and high energy density and makes it possible for practical
applications.
■
EXPERIMENTAL SECTION
Synthesis of HC. Chitosan (degree of deacetylation ≥95%,
viscosity 100−200 MPa·s, Aladdin Co.,) was used without further
purification for preparation of HC by pyrolysis. It was carbonized at
1100 °C for 2 h in the N2 atmosphere using a quartz glass tube
furnace. The yield is 30%.
Material Characterization. The morphology of produced
materials was investigated using Hitachi S-4800 (Japan) scanning
electron microscopy (SEM). Transmission electron microscopy
(TEM) was performed on JEOL-JEM-2100F (Japan). X-ray
diffraction (XRD) was conducted on Bruker-D8 ADVANCE
(Germany) with a Cu Kα radiation source (V = 40 kV, I = 40 mA,
and λ = 1.5418 Å). Raman spectroscopy was carried out on a Thermo
Fisher Scientific-DXR (USA) with a 532 nm laser. CO2 adsorption−
desorption isotherms were measured on a Micromeritics ASAP 2420-
4 volumetric adsorption analyzer (USA). X-ray photoelectron
spectroscopy (XPS) was carried out on EDAX-GENESIS (USA)
with a mono Al Kα radiation.
Electrochemical Measurement. The HC anodes were prepared
by casting the slurry consisting of 90 wt % HC powder and 10 wt %
sodium alginate binder (in a 10 mg/mL aqueous solution) on Cu foils
and dried at 110 °C in a vacuum oven overnight. The HC anodes
with different mass loadings of 1.5, 5.0, 7.0, 12.0, and 17.0 mg/cm2
were prepared. CR2032 type coin cells were assembled in an argon-
filled glovebox (Mikrouna, universal 2440, China) with H2O and O2 <
0.1 ppm. Sodium metal (Na, Sigma-Aldrich, USA) was used as
counter and reference electrodes. The ether-based electrolyte is 1 M
NaPF6 in ethylene glycol dimethyl ether (DME), and the ester-based
electrolyte is 1 M NaClO4 in a mixture of ethylene carbonate (EC)
and dimethyl carbonate (DMC) (1:1, v/v). The ionic conductibility
was measured at 25 °C using an ionic conductivity meter DDSJ-308A
(Shanghai Hongyi Instrument Co. Ltd.).
The galvanostatic discharge/charge cycling performance was tested
on LAND CT2001A battery testers at a voltage range of 0−2.5 V
versus Na+/Na. Cyclic voltammetry (CV) measurements were carried
out on a CHI 600 electrochemical test station at a scan rate of 0.1
mV/s between 0 and 2.5 V. Electrochemical impedance spectroscopy
(EIS) measurements were conducted on a frequency response
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analyzer (Solartron, SI 1260) in the frequency range from 0.01 to 106
Hz with an AC signal amplitude of 5 mV.
■ RESULTS AND DISCUSSION
HC was synthesized by directly pyrolyzing chitosan in the N2
atmosphere (Figure S1). The morphology of the HC was
examined by SEM and high-resolution TEM (HRTEM). As
shown in Figure 1a, the HC has a random granular shape with
a particle size of <10 μm. The HRTEM image (Figure 1b)
indicates an amorphous structure, a typical feature of HC,
consisting of numerous randomly oriented and locally ordered
nanocrystallites and micropores. The interlayer spacing within
the nanocrystallites is measured to be 0.363 nm, larger than
that of graphite (0.335 nm). The expanded interlayer spacing
should be induced by the incorporation of heteroatoms of
oxygen and nitrogen and/or defective carbon structures.45−47
The randomly oriented structure was further confirmed by the
XRD pattern shown in Figure 1c, where only broad peaks at 2θ
= 24.4° and 43.3° are presented [corresponding to (002) and
(101) planes, respectively], indicative of an amorphous
structure. The average interlayer distance was calculated to
be 0.366 nm, consistent with the observation by HRTEM
(Figure 1b). The Raman spectrum of the HC also reveals the
amorphous and crystallite structures by two broad peaks at
1361 and 1595 cm−1 (Figure 1d), which corresponds to the D-
band of defects and the G-band of graphitic carbon,
respectively. This is in good agreement with the HRTEM
and XRD measurement results. The porous structure of the
HC was investigated by CO2 adsorption measurement (Figure
S2). A low specific surface area of 47.6 m2/g was measured,
which is in favor of reducing the formation of SEI layers and
thus improves the ICE of HC anodes.48,49
XPS was performed to analyze the element composition and
the chemical states of the HC. C 1s, N 1s, and O 1s peaks were
detected at 284.6, 401.4, and 531.4 eV in the XPS survey
spectrum with the atomic contents of 93.7, 1.4, and 4.9%,
respectively (Figure S3 and Table S1). The high-resolution
spectrum of the C 1s peak can be fitted into four peaks of sp2 C
(284.5 eV), −CH2− (284.9 eV), C−O (286.0 eV), CO
(287.3 eV), and OC−O (289.2 eV) bonds (Figure 1e).50
The high-resolution O 1s core-level spectrum was deconvo-
luted into two peaks at 531.3 and 532.6 eV (Figure 1f),
corresponding to CO and C−O bonds, respectively.50 The
N consists of three different circumstances: pyridinic N (N-6)
at 398.4 eV, pyrrolic N (N-5) at 400.9 eV, and quaternary N
(N-Q) at 401.4 eV (Figure 1g).50−52 The quaternary N can
increase the conductivity of carbon materials as a result of the
introduction of extra free electrons, whereas N-5 and N-6 can
adsorb exotic atoms, thus functioning as Na storage sites.52,53
In order to explore the electrochemical performance of the
HC, it was evaluated in half coin cells using an ether-based
electrolyte of 1 M NaPF6 in ethylene glycol DME with a mass
loading of 1.5 mg/cm2. Figure 2a shows the galvanostatic
discharge/charge (sodiation/desodiation) profiles of the HC
anodes in the initial three cycles at a current density of 0.02 A/
g and a voltage window of 0−2.5 V versus Na+/Na. A high-
voltage slope (>0.1 V) followed by a plateau below 0.1 V was
displayed, which is a characteristic behavior of HC anode
materials in NIBs. The high-voltage sloping region is attributed
to sodium adsorption on the defect sites or heteroatoms,
whereas the low-voltage plateau corresponds to sodium filling
into the micropores.54,55 Micropores with pore sizes of <0.8
nm were clearly measured (Figure S2b). According to our
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Figure 2. Electrochemical performance: (a) galvanostatic discharge/
charge profiles, (b) cyclic voltammogram curves at a scanning rate of
0.1 mV/s, and cycling performance at (c) 0.05, and (d) 2 A/g of the
HC anodes.
previous work, where the pore-filling mechanism at the low-
voltage plateau was clearly verified, the plateau capacity in this
work is attributed to the insertion of Na+ in the micropores. A
high reversible capacity of 275.4 mA h/g was delivered with an
ICE of 85.9%, which is among the best HC anodes reported in
the literature (Table S2). Besides the extremely low specific
surface area of the HC material (47.6 m2/g), the utilization of
the ether-based electrolyte was in favor of increasing the ICEs
of the HC anodes in NIBs.48,49 The ICE of the HC anodes is
75.0% in the ester-based electrolyte, much lower than that in
the ether-based electrolyte. The enhanced ICE in the ether-
based electrolyte should be resulted from the less decom-
position of the electrolyte to form thinner SEI films on the HC
surface compared with that in the ester-based electrolyte.38,39
The CV curves were collected at a scanning rate of 0.1 mV/s
and in the voltage window of 0−2.5 V (Figure 2b). A strong
reversible redox couple at 0.06/0.10 V should result from the
pore filling process, and a small irreversible peak at 0.59 V in
the first cathodic process was assigned to the formation of SEI
layers on the electrode surface and disappeared in the
following cycles.55 The overlapped desodiation curves in
both galvanostatic discharge/charge and CV measurements
strongly suggest a high reversibility of HC anodes.
The cycling stability of the HC anodes was first examined at
a current density of 50 mA/g. After a slight capacity decline in
the initial few cycles, no further capacity decay was observed
up to 300 cycles (Figure 2c), demonstrating an exceptional
stability. This is further confirmed by 90% capacity retention
(196 mA h/g) after 2000 cycles at 1 A/g (Figure 2d). The
galvanostatic discharge/charge voltage profiles of the HC
anodes in selected cycles are shown in Figure S4. The
performance outperforms all those HC anodes for NIBs ever
reported in the literature (Table S2).
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Figure 3. Comparison of the rate behavior of the HC electrodes in ether- and ester-based electrolytes: (a) rate performance of the HC electrodes at
symmetric discharge/charge current rates, the discharge/charge voltage profiles in the symmetric current rates with (b) ether-based electrolyte and
(c) ester-based electrolyte, analysis of the sloping and plateau region capacity contribution with (d) ether-based electrolyte and (e) ester-based
electrolyte, the discharge/charge voltage profiles at a low discharge current of 0.02 A/g and different charge currents with (f) ether-based
electrolyte and (g) ester-based electrolyte, and (h) capacity retention and (i) overpotential at a discharge rate of 0.02 A/g and different charge
current rates.

The rate capability of the HC anodes was evaluated at
different discharge/charge current densities from 0.02 to 10 A/
g with the ether-based electrolyte. For comparison, the HC
electrodes were also tested in the same conditions except for
the use of an ester-based electrolyte of 1 M NaClO4 in EC and
DMC (1:1, v/v), a commonly used electrolyte for NIBs in the
literature (Figure 3a). The corresponding discharge/charge
profiles were shown in Figure 3b for the ether-based electrolyte
and Figure 3c for the ester-based electrolyte. The HC anodes
exhibited an extraordinary rate capability with a high capacity
retention of 206 mA h/g at a current rate of 2 A/g in the ether-
based electrolyte and 139 mA h/g even at a very high current
density of 10 A/g (equal to 51% capacity retention of that at
0.02 A/g). Such high capacity retention has never been
reported for HC anode materials in NIBs (Figure S5). In
contrast, with the ester-based electrolyte, the capacity suffers a
fast capacity scroll-off as the current density increases and only
60 mA h/g is remained at 2 A/g, which is in agreement with
those previous reports.31,53 Note that the similar reversible
capacities at low current rates suggest that the Na storage in
the HC is thermodynamically the same in the two kinds of
electrolytes but is kinetically controlled at higher current
densities as shown by the huge gap in capacities. As current
density increases, the capacity fading mainly comes from the
sloping region in the ether-based electrolyte but the plateau
region in the ester-based electrolyte (Figure 3d,e), which
clearly reveals the significant kinetics difference between the
two electrolytes.
The rate capability was examined by sodiating at a low rate
of 0.02 A/g to make sure a complete sodiation reaction but
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desodiating at different rates (Figure 3f,g). Surprisingly,
different from the rate performance obtained with symmetric
sodiation/desodiation current densities (Figure 3b,c), similar
desodiation capacities were delivered in the two kinds of
electrolytes in the asymmetric current rate tests (Figure 3h),
215.9 mA h/g for the ether-based electrolyte and 206.2 mA h/
g for the ester-based electrolyte at 5 A/g. The difference
between the two test protocols is attributed to the large
desodiation voltage window (ΔVdes, voltage difference between
average desodiation voltage of the plateau at 0.02 A/g and
cutoff voltage) and the small sodiation voltage window (ΔVsod,
voltage difference between average sodiation voltage of the
plateau at 0.02 A/g and cutoff voltage) as well as the kinetics
difference in the two electrolytes (Table S3). ΔVsod is 0.071
and 0.079 V for the ether-based and ester-based electrolytes,
respectively. It can be seen from Figure 3i that the
overpotential (η) at high current rates is much larger for the
ester-based electrolyte than the ether-based electrolyte (Table
S4). Taking the plateau voltage at 0.02 A/g as a baseline
(0.079 and 0.071 V, respectively), η at 5 A/g is 0.654 V for the
ester-based electrolyte, whereas it is only 0.088 V for the ether-
based electrolyte. If η < ΔVsod, the HC anodes can be
completely sodiated, whereas in the case of η > ΔVsod, Na ions
are difficult to insert into the HC. Assuming that the
overpotentials for sodiation and desodiation are same at the
same current rates, at 1.0 A/g, η is 0.116 V in the ester-based
electrolyte, larger than Δsod (0.091 V), leading to an
incomplete Na ion insertion and thereby lower sodiation
capacity (Figure 3i). In the ether-based electrolyte, η is small
even at 10 A/g (0.167 V), enabling an efficient sodiation
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Figure 4. Kinetics characterization of the HC electrode in ether- and ester-based electrolytes. (a) Nyquist plots and fitting curves after several
cycles (both at 1.8 V). The hollow circles show the experimental data and lines represent the fitting results, respectively. Morphology observed by
SEM in (b) ether- and (c) ester-based electrolyte after 100 cycles. Scale bar, 5 μm. (d) Wettability of ether- and ester-based electrolytes on the HC
electrodes. (e) Logarithm diffusion coefficient (log D) at different states of charge in discharge and charge process.
reaction and thus a high capacity. During the desodiation
processes, ΔVdes is large enough to tolerate even at a high
current rate. As a result, a complete desodiation will occur
either in ether- or ester-based electrolytes and thus a high
capacity retention upon a complete sodiation.
The disparate overpotentials in the two electrolytes depend
on the significant different reaction kinetics. The reaction
kinetics of the HC anodes in the two electrolytes was
investigated using EIS to account for the rate of Na+ ions in
electrolytes and passing through the SEI films. Figure 4a
compares the Nyquist plots of two electrolytes. The impedance
is much smaller in the ether-based electrolyte than that in the
ester-based electrolyte, indicating a faster kinetics in the former
one. The impedance data were fitted with equivalent circuits as
shown in Figure S6. The resistance of Rs represents the
electrolyte resistance and Rct and Rf correspond to the charge
transfer resistance and the contact resistance related to the SEI
layers, respectively. The electrolyte resistance (Rs) is 4.6 Ω in
the ether-based electrolyte and 5.3 Ω in the ester-based
electrolyte, showing a higher ion movability in the ether-based
electrolyte. This is also consistent with the ionic conductivity
test results by a test meter, where the ether-based electrolyte
has a Na+ ionic conductivity of 15.6 mS/cm much larger than
that of 8.6 mS/cm of the ester-based electrolyte. The charge
transfer resistance (Rct) is mainly associated with the electronic
conductivity and the ionic diffusion coefficient. Therefore,
higher ionic diffusion coefficient of the ether-based electrolyte
responds to the smaller Rct. The smaller contact resistance (Rf)
in the ether-based electrolyte is verified by the thinner SEI
layers formed on the electrode surface, confirmed by SEM
images which still clearly show the HC particle shapes without
any distinct shroud after 100 cycles (Figure 4b) compared with
the pristine electrolyte (Figure S7). Surprisingly, the surface of
the electrolyte shows less change of outline of the HC particles
even after 2000 cycles (Figure S8). In contrast, the HC
particles are encapsulated by a thick SEI layer and can be
difficult to discern in the ester-based electrolyte after 100
cycles (Figure 4c). These demonstrate a thin and sustainable
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SEI layer in the ether-based electrolyte. The chemical property
of the SEI films formed in the two different electrolytes was
investigated by XPS (Figure S9). The SP2 C peak is relatively
weaker and the O−CO/CO and Na−O peaks are
stronger in the EC/DMC electrolyte-originated SEI films
than in the DME electrolyte-originated SEI films, indicating
that a larger amount of decomposition products were produced
in the ester-based electrolyte, in accordance with a thicker SEI
film.38,40
The reaction kinetics of HC in different electrolytes also
depends on the wettability of the electrolyte with HC
electrodes. It has been reported that the interaction between
the electrode materials and the electrolytes may produce
significant effects on the formation of SEI layers and thus the
electrochemical performance.56−59 In our case, the wettability
of HC electrodes was tested with the two kinds of electrolytes
(Figure 4d). The ether-based electrolyte can fully wet the HC
electrodes as shown by the rapid spread upon the contact with
the electrolytes (contact angles nearly 0°). In contrast, the
ester-based electrolyte presents a contact angle of 33.1°,
indicating a poor wettability. The better wettability suggests a
stronger interaction between the electrolytes and the electro-
des, benefiting the formation of a thin and sustainable SEI layer
and thus reducing the interfacial resistance.60
The reaction kinetics of HC in different electrolytes lies on
the diffusion kinetics as well. To further evaluate Na+ ion
diffusion properties in the HC particles with the two
electrolytes, the Na+ ion diffusion coefficient (DNa+) at different
sodiation/desodiation states were calculated using the
Warburg diffusion in the low-frequency linear region of
EIS.61,62 The computation is described in the Supporting
Information. DNa+ in the ether-based electrolyte (∼10−14) is
found to be an order of magnitude higher than that of the
ester-based electrolyte (∼10−15) (Figure 4e), meaning a much
faster transfer of Na+ ions within the HC particles when the
ether-based electrolyte is used. The use of the ether-based
electrolyte affords a higher ionic conductivity, produces a
thinner SEI layer, offers a larger ion diffusion coefficient, and
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finally results in an outstanding rate capability. The sodiation
and desodiation behaviors of the HC anodes in the ether- and
ester-based electrolytes are schematically illustrated in Figure
5.
Figure 5. Schematic illustration of the kinetics in HC anode for NIBs.
To verify the improved sodiation and desodiation kinetics in
the ether-based electrolyte, HC electrodes with different mass
loadings were fabricated from a common value of 1.5 mg/cm2
to an ultrahigh value of 17 mg/cm2 (Figure S10a). The
excellent electrochemical performance and outstanding rate
capability of the HC anode in the ether-based electrolyte with
high ionic conductivity and superior wettability make the high
mass-loading electrodes possible for practical commercial
applications. The thicknesses of the HC anodes were measured
to be 14 μm for 1.5 mg/cm2, 47 μm for 5.0 mg/cm2, 65 μm for
7.0 mg/cm2, 117 μm for 12 mg/cm2, and 195 μm for 17 mg/
cm2, respectively (Figure S10b,c), indicating a proportional
correlation between the thickness and the mass loading. The
photographs and SEM images of the electrodes with different
mass loadings reveal a similar surface morphology, showing
Figure 6. Electrochemical performance of the HC anodes with different mass loadings with the ether-based electrolyte: (a) galvanostatic discharge/
charge profiles at a current density of 0.02 A/g, (b) gravimetric and areal specific capacities, (c) initial Coulombic efficiencies at 0.02 A/g, and (d)
cycling performance at a current density of 0.2 A/g after 2 cycle activation at 0.02 A/g.
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that the mass-loading variation does not inflict obvious
influence on the film quality of the HC electrodes. The
uniformity of the electrodes with different thicknesses was
further confirmed by the cross-sectional SEM images (Figure
S10d). A compact and uniform distribution of the active
material was displayed for all electrodes even for the ultrahigh
mass loading of 17 mg/cm2. Such high mass loading has never
been reported for HC anodes in NIBs and it is comparable
with those of commercial graphite anodes in LIBs (15 mg/
cm2), which promises commercial applications for high energy
NIBs.29,43
In order to prove the feasibility of high mass loading in NIBs
with HC anodes, the electrochemical performance of the HC
anodes with different mass loadings was evaluated by the
galvanostatic discharge/charge test at the current density of
0.02 A/g. Typical HC voltage profiles are displayed for all
mass-loading anodes with a voltage slope at high voltage (>0.1
V) followed by a voltage plateau below 0.1 V (Figure 6a).
Surprisingly, high reversible capacities of >250 mA h/g were
delivered for all mass-loading electrodes and a high areal
specific capacity of 4.3 mA h/cm2 can be achieved (Figure 6b)
with a very high ICE of 85.4% (Figure 6c), which are among
the highest values for the HC anodes in NIBs (Table S2). The
thickness and electrochemical performance of the HC anodes
with different mass loadings are summarized in Table S5. The
good electrochemical performance of the HC electrodes with
high mass loadings is unquestionably attributed to the
enhanced electronic conductivity of the nitrogen-doping HC
and the outstanding kinetics boosted by the ether-based
electrolyte. The cycling stability of the HC anodes with
different mass loadings was tested at 0.2 A/g after two
activation cycles at 0.02 A/g (Figure 6d). Stable cycling
performance was demonstrated for all electrodes with
negligible capacity loss over 150 cycles. The surface
morphology and structure of the electrodes after the cycling
test were examined using photomicroscopy and SEM (Figure
S11). No obvious morphology change and structure
degradation happened except for a thickness increase by
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<10% for all mass-loading HC anodes, showing a sustainability
of the HC electrodes even at a high mass loading of 17 mg/
cm2.
■ CONCLUSIONS
A compatible electrolyte strategy is investigated to enhance the
electrochemical performance of the HC anodes in NIBs
toward practical applications. The results show that the better
compatibility between the ether-based electrolytes and the HC
anodes, such as better wettability, formation of thinner and
sustainable SEI films, higher ionic conductivity, and high ion
diffusion coefficient in HC, plays an important role in
improving performance of HC anodes compared with the
ester-based electrolytes. These account for the long cycle life
and high rate performance of the HC anodes. With the
enhanced kinetics, a high reversible areal capacity of 4.3 mA h/
cm2 was achieved, preeminent to all those reported HC anodes
in the literature. Our findings shed light on the system design
of NIBs from the electrolyte strategies with superior kinetics
and high energy density, which make NIBs with HC anodes
possible for practical applications in large-scale energy storage.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.8b15274.
Schematic synthesis process of HC, XPS survey
spectrum of the HC , adsorption pore distribution and
CO2 adsorption isotherms of HC , galvanostatic
discharge/charge profiles of the HC anodes from the
10th to 2000th cycles , rate performance comparison ,
Nyquist plots and fitting curves in ether- and ester-based
electrolytes, SEM image of the pristine HC electrodes,
SEM image of the HC electrode after 2000 cycles in the
ether-based electrolyte, XPS C 1s, O 1s, and Na 1s core-
level spectra for the HC electrodes cycled in different
electrolytes, photographs and SEM images of the
pristine HC electrodes and after 50 cycles with different
mass loadings in the ether-based electrolyte, XPS surface
elemental atomic components of the HC, electro-
chemical performance comparison, average desodiation
plateau voltages of the HC anodes, overpotentials of the
HC anodes, electrochemical performance of HC anodes
with different mass loadings, and Computational process
(DNa+ diffusion coefficient calculation) (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: shuyangao@htu.cn (S.G.).
*E-mail: yunhua.xu@tju.edu.cn (Y.X.).
ORCID
Shuyan Gao: 0000-0001-5221-6645
Yunhua Xu: 0000-0003-1818-3661
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors gratefully acknowledge the support of the
National Natural Science Foundation of China (grant no.:
51672188), Natural Science Foundation of Tianjin City (grant
no.: 16JCYBJC40900), and the Thousand Talents Plan for
41386
Research Article
Young Professionals of China. The authors thank Dr. J. Jiang
and C. Zhang (Shanxi Normal University) for the help on the
gas adsorption/desorption analysis.
■ REFERENCES
(1) Goodenough, J. B.; Park, K.-S. The Li-Ion Rechargeable Battery:
A Perspective. J. Am. Chem. Soc. 2013, 135, 1167−1176.
(2) Yabuuchi, N.; Kubota, K.; Dahbi, M.; Komaba, S. Research
Development on Sodium-Ion Batteries. Chem. Rev. 2014, 114,
11636−11682.
(3) Xu, G.-L.; Amine, R.; Abouimrane, A.; Che, H.; Dahbi, M.; Ma,
Z.-F.; Saadoune, I.; Alami, J.; Mattis, W. L.; Pan, F.; Chen, Z.; Amine,
K. Challenges in Developing Electrodes, Electrolytes, and Diagnostics
Tools to Understand and Advance Sodium-Ion Batteries. Adv. Energy
Mater. 2018, 8, 1702403.
(4) Stevens, D. A.; Dahn, J. R. The Mechanisms of Lithium and
Sodium Insertion in Carbon Materials. J. Electrochem. Soc. 2001, 148,
A803.
(5) Jache, B.; Adelhelm, P. Use of Graphite as a Highly Reversible
Electrode with Superior Cycle Life for Sodium-Ion Batteries by
Making Use of Co-Intercalation Phenomena. Angew. Chem., Int. Ed.
2014, 53, 10169−10173.
(6) Yan, Y.; Yin, Y.-X.; Guo, Y.-G.; Wan, L.-J. A Sandwich-Like
Hierarchically Porous Carbon/Graphene Composite as a High-
Performance Anode Material for Sodium-Ion Batteries. Adv. Energy
Mater. 2014, 4, 1301584.
(7) Cao, Y.; Xiao, L.; Sushko, M. L.; Wang, W.; Schwenzer, B.; Xiao,
J.; Nie, Z.; Saraf, L. V.; Yang, Z.; Liu, J. Sodium Ion Insertion in
Hollow Carbon Nanowires for Battery Applications. Nano Lett. 2012,
12, 3783−3787.
(8) Li, W.; Zeng, L.; Yang, Z.; Gu, L.; Wang, J.; Liu, X.; Cheng, J.;
Yu, Y. Free-standing and Binder-free Sodium-ion Electrodes with
Ultralong Cycle Life and High Rate Performance Based on Porous
Carbon Nanofibers. Nanoscale 2014, 6, 693−698.
(9) Bommier, C.; Surta, T. W.; Dolgos, M.; Ji, X. New Mechanistic
Insights on Na-Ion Storage in Nongraphitizable Carbon. Nano Lett.
2015, 15, 5888−5892.
(10) Zhang, S.-W.; Lv, W.; Luo, C.; You, C.-H.; Zhang, J.; Pan, Z.-
Z.; Kang, F.-Y.; Yang, Q.-H. Commercial Carbon Molecular Sieves as
a High Performance Anode for Sodium-ion Batteries. Energy Storage
Mater. 2016, 3, 18−23.
(11) Li, Y.; Hu, Y.-S.; Qi, X.; Rong, X.; Li, H.; Huang, X.; Chen, L.
Advanced Sodium-ion Batteries Using Superior Low Cost Pyrolyzed
Anthracite Anode: Towards Practical Applications. Energy Storage
Mater 2016, 5, 191−197.
(12) Zhu, Y.; Han, X.; Xu, Y.; Liu, Y.; Zheng, S.; Xu, K.; Hu, L.;
Wang, C. Electrospun Sb/C Fibers for a Stable and Fast Sodium-Ion
Battery Anode. ACS NanoAcs Nano 2013, 7, 6378−6386.
(13) Liu, J.; Yu, L.; Wu, C.; Wen, Y.; Yin, K.; Chiang, F.-K.; Hu, R.;
Liu, J.; Sun, L.; Gu, L.; Maier, J.; Yu, Y.; Zhu, M. New Nanoconfined
Galvanic Replacement Synthesis of Hollow Sb@C Yolk-Shell Spheres
Constituting a Stable Anode for High-Rate Li/Na-Ion Batteries. Nano
Lett. 2017, 17, 2034−2042.
(14) Qian, J.; Wu, X.; Cao, Y.; Ai, X.; Yang, H. High Capacity and
Rate Capability of Amorphous Phosphorus for Sodium Ion Batteries.
Angew. Chem.andte Chemie 2013, 125, 4731−4734.
(15) Zhu, Y.; Wen, Y.; Fan, X.; Gao, T.; Han, F.; Luo, C.; Liou, S.-
C.; Wang, C. Red Phosphorus Single-Walled Carbon Nanotube
Composite as a Superior Anode for Sodium Ion Batteries. ACS
NanoAcs Nano 2015, 9, 3254−3264.
(16) Xu, Y.; Liu, Q.; Zhu, Y.; Liu, Y.; Langrock, A.; Zachariah, M. R.;
Wang, C. Uniform Nano-Sn/C Composite Anodes for Lithium Ion
Batteries. Nano Lett. 2013, 13, 470−474.
(17) Xu, Y.; Zhu, Y.; Liu, Y.; Wang, C. Electrochemical Performance
of Porous Carbon/Tin Composite Anodes for Sodium-Ion and
Lithium-Ion Batteries. Adv. Energy Mater. 2013, 3, 128−133.
(18) Wang, C.; Wang, L.; Li, F.; Cheng, F.; Chen, J. Bulk Bismuth as
a High-Capacity and Ultralong Cycle-Life Anode for Sodium-Ion
DOI: 10.1021/acsami.8b15274
ACS Appl. Mater. Interfaces 2018, 10, 41380−41388
ACS Applied Materials & Interfaces
Batteries by Coupling with Glyme-Based Electrolytes. Adv. Mater.
2017, 29, 1702212.
(19) Yabuuchi, N.; Kajiyama, M.; Iwatate, J.; Nishikawa, H.; Hitomi,
S.; Okuyama, R.; Usui, R.; Yamada, Y.; Komaba, S. P2-type
Nax[Fe1/2Mn1/2]O2 Made from Earth-abundant Elements for
Rechargeable Na batteries. Nat. Mater. 2012, 11, 512−517.
(20) Zhang, Y.; Foster, C. W.; Banks, C. E.; Shao, L.; Hou, H.; Zou,
G.; Chen, J.; Huang, Z.; Ji, X. Graphene-Rich Wrapped Petal-Like
Rutile TiO2 tuned by Carbon Dots for High-Performance Sodium
Storage. Adv. Mater. 2016, 28, 9391−9399.
(21) Hu, Z.; Zhu, Z.; Cheng, F.; Zhang, K.; Wang, J.; Chen, C.;
Chen, J. Pyrite FeS2 for High-rate and Long-life Rechargeable Sodium
Batteries. Energy Environ. Sci. 2015, 8, 1309−1316.
(22) Liu, Z.; Lu, T.; Song, T.; Yu, X.-Y.; Lou, X. W.; Paik, U.
Structure-designed Synthesis of FeS2@C Yolk-shell Nanoboxes as a
High-performance Anode for Sodium-ion Batteries. Energy Environ.
Sci. 2017, 10, 1576−1580.
(23) Pan, Z.-Z.; Yan, Y.; Cui, N.; Xie, J.-C.; Zhang, Y.-B.; Mu, W.-S.;
Hao, C. Ionic Liquid-Assisted Preparation of Sb2S3/Reduced
Graphene Oxide Nanocomposite for Sodium-Ion Batteries. Adv.
Mater. Interfaces 2018, 5, 1701481.
(24) Wang, S.; Wang, L.; Zhu, Z.; Hu, Z.; Zhao, Q.; Chen, J. All
Organic Sodium-Ion Batteries with Na4C8H2O6. Angew. Chem., Int.
Ed. 2014, 126, 6002−6006.
(25) Wu, X.; Jin, S.; Zhang, Z.; Jiang, L.; Mu, L.; Hu, Y.-S.; Li, H.;
Chen, X.; Armand, M.; Chen, L.; Huang, X. Unraveling the Storage
Mechanism in Organic Carbonyl Electrodes for Sodium-ion Batteries.
Sci. Adv. 2015, 1, No. e1500330.
(26) Stevens, D. A.; Dahn, J. R. High Capacity Anode Materials for
Rechargeable Sodium-Ion Batteries. J. Electrochem. Soc. 2000, 147,
1271.
(27) Li, H.; Shen, F.; Luo, W.; Dai, J.; Han, X.; Chen, Y.; Yao, Y.;
Zhu, H.; Fu, K.; Hitz, E.; Hu, L. Carbonized-leaf Membrane with
Anisotropic Surfaces for Sodium-ion Battery. ACS Appl. Mater.
Interfaces 2016, 8, 2204−2210.
(28) Lotfabad, E. M.; Ding, J.; Cui, K.; Kohandehghan, A.;
Kalisvaart, W. P.; Hazelton, M.; Mitlin, D. High-Density Sodium
and Lithium Ion Battery Anodes from Banana Peels. ACS Nano 2014,
8, 7115−7129.
(29) Ding, J.; Wang, H.; Li, Z.; Cui, K.; Karpuzov, D.; Tan, X.;
Kohandehghan, A.; Mitlin, D. Peanut Shell Hybrid Sodium Ion
Capacitor with Extreme Energy-power Rivals Lithium Ion Capacitors.
Energy Environ. Sci. 2015, 8, 941−955.
(30) Gao, S.; Li, X.; Li, L.; Wei, X. A Versatile Biomass Derived
Carbon Material for Oxygen Reduction Reaction, Supercapacitors and
Oil/water Separation. Nano Energy 2017, 33, 334−342.
(31) Sun, N.; Liu, H.; Xu, B. Facile Synthesis of High Performance
Hard Carbon Anode Materials for Sodium Ion Batteries. J. Mater.
Chem. A 2015, 3, 20560−20566.
(32) Li, Y.; Hu, Y.-S.; Titirici, M.-M.; Chen, L.; Huang, X. Hard
Carbon Microtubes Made from Renewable Cotton as High-
Performance Anode Material for Sodium-Ion Batteries. Adv. Energy
Mater. 2016, 6, 1600659.
(33) Ding, J.; Wang, H.; Li, Z.; Kohandehghan, A.; Cui, K.; Xu, Z.;
Zahiri, B.; Tan, X.; Lotfabad, E. M.; Olsen, B. C.; Mitlin, D. Carbon
Nanosheet Frameworks Derived from Peat Moss as High Perform-
ance Sodium Ion Battery Anodes. ACS Nano 2013, 7, 11004−11015.
(34) Liu, P.; Li, Y.; Hu, Y.-S.; Li, H.; Chen, L.; Huang, X. A Waste
Biomass Derived Hard Carbon as a High-performance Anode
Material for Sodium-ion Batteries. J. Mater. Chem. A 2016, 4,
13046−13052.
(35) Wang, P.; Zhu, X.; Wang, Q.; Xu, X.; Zhou, X.; Bao, J. Kelp-
derived Hard Carbons as Advanced Anode Materials for Sodium-ion
Batteries. J. Mater. Chem. A 2017, 5, 5761−5769.
(36) Zhang, F.; Yao, Y.; Wan, J.; Henderson, D.; Zhang, X.; Hu, L.
High Temperature Carbonized Grass as a High Performance Sodium
Ion Battery Anode. ACS Appl. Mater. Interfaces 2017, 9, 391−397.
41387
Research Article
(37) Zheng, Y.; Wang, Y.; Lu, Y.; Hu, Y.-S.; Li, J. A high-
performance Sodium-ion Battery Enhanced by Macadamia Shell
Derived Hard Carbon Anode. Nano Energy 2017, 39, 489−498.
(38) Zhang, J.; Wang, D.-W.; Lv, W.; Zhang, S.; Liang, Q.; Zheng,
D.; Kang, F.; Yang, Q.-H. Achieving Superb Sodium Storage
Performance on Carbon Anodes Through an Ether-derived Solid
Electrolyte Interphase. Energy Environ. Sci. 2017, 10, 370−376.
(39) Zhu, Y.-E.; Yang, L.; Zhou, X.; Li, F.; Wei, J.; Zhou, Z. Boosting
the Rate Capability of Hard Carbon With an Ether-based Electrolyte
for Sodium Ion Batteries. J. Mater. Chem. A 2017, 5, 9528−9532.
(40) Bai, P.; He, Y.; Xiong, P.; Zhao, X.; Xu, K.; Xu, Y. Long Cycle
Life And High Rate Sodium-ion Chemistry for Hard Carbon Anodes.
Energy Storage Mater 2018, 13, 274−282.
(41) Luo, W.; Schardt, J.; Bommier, C.; Wang, B.; Razink, J.;
Simonsen, J.; Ji, X. Carbon Nanofibers Derived from Cellulose
Nanofibers as a Long-life Anode Material for Rechargeable Sodium-
ion Batteries. J. Mater. Chem. A 2013, 1, 10662−10666.
(42) Zhou, D.; Peer, M.; Yang, Z.; Pol, V. G.; Key, F. D.; Jorne, J.;
Foley, H. C.; Johnson, C. S. Long Cycle Life Microporous Spherical
Carbon Anodes for Sodium-ion Batteries Derived from Furfuryl
Alcohol. J. Mater. Chem. A 2016, 4, 6271−6275.
(43) Johnson, B. A.; White, R. E. Characterization of Commercially
Available Lithium-ion Batteries. J. Power Sources 1998, 70, 48−54.
(44) Liu, N.; Lu, Z.; Zhao, J.; McDowell, M. T.; Lee, H.-W.; Zhao,
W.; Cui, Y. A Pomegranate-inspired Nanoscale Design for Large-
volume-change Lithium Battery Anodes. Nat. Nanotechnol. 2014, 9,
187−192.
(45) Wen, Y.; He, K.; Zhu, Y.; Han, F.; Xu, Y.; Matsuda, I.; Ishii, Y.;
Cumings, J.; Wang, C. Expanded Graphite as Superior Anode for
Sodium-ion Batteries. Nat. Commun. 2014, 5, 4033.
(46) Yang, T.; Qian, T.; Wang, M.; Shen, X.; Xu, N.; Sun, Z.; Yan, C.
A Sustainable Route from Biomass Byproduct Okara to High Content
Nitrogen-Doped Carbon Sheets for Efficient Sodium Ion Batteries.
Adv. Mater. 2016, 28, 539−545.
(47) Xiao, L.; Lu, H.; Fang, Y.; Sushko, M. L.; Cao, Y.; Ai, X.; Yang,
H.; Liu, J. Low-Defect and Low-Porosity Hard Carbon with High
Coulombic Efficiency and High Capacity for Practical Sodium Ion
Battery Anode. Adv. Energy Mater. 2018, 8, 1703238.
(48) Luo, W.; Bommier, C.; Jian, Z.; Li, X.; Carter, R.; Vail, S.; Lu,
Y.; Lee, J.-J.; Ji, X. Low-Surface-Area Hard Carbon Anode for Na-Ion
Batteries via Graphene Oxide as a Dehydration Agent. ACS Appl.
Mater. Interfaces 2015, 7, 2626−2631.
(49) Li, Y.; Xu, S.; Wu, X.; Yu, J.; Wang, Y.; Hu, Y.-S.; Li, H.; Chen,
L.; Huang, X. Amorphous Monodispersed Hard Carbon Micro-
spherules Derived from Biomass as a High Performance Negative
Electrode Material for Sodium-ion Batteries. J. Mater. Chem. A 2015,
3, 71−77.
(50) Cong, H.-P.; Ren, X.-C.; Wang, P.; Yu, S.-H. Flexible
Graphene-polyaniline Composite Paper for High-performance Super-
capacitor. Energy Environ. Sci. 2013, 6, 1185−1191.
(51) Ling, Z.; Yu, C.; Fan, X.; Liu, S.; Yang, J.; Zhang, M.; Wang, G.;
Xiao, N.; Qiu, J. Freeze-drying for Sustainable Synthesis of Nitrogen
Doped Porous Carbon Cryogel with Enhanced Supercapacitor and
Lithium Ion Storage Performance. Nanotechnology 2015, 26, 374003.
(52) Hao, R.; Yang, Y.; Wang, H.; Jia, B.; Ma, G.; Yu, D.; Guo, L.;
Yang, S. Direct Chitin Conversion to N-doped Amorphous Carbon
Nanofibers for High-performing Full Sodium-ion Batteries. Nano
Energy 2018, 45, 220−228.
(53) Huang, S.; Li, Z.; Wang, B.; Zhang, J.; Peng, Z.; Qi, R.; Wang,
J.; Zhao, Y. N-Doping and Defective Nanographitic Domain Coupled
Hard Carbon Nanoshells for High Performance Lithium/Sodium
Storage. Adv. Funct. Mater. 2018, 28, 1706294.
(54) Zhang, B.; Ghimbeu, C. M.; Laberty, C.; Vix-Guterl, C.;
Tarascon, J.-M. Correlation Between Microstructure and Na Storage
Behavior in Hard Carbon. Adv. Energy Mater. 2016, 6, 1501588.
(55) Bai, P.; He, Y.; Zou, X.; Zhao, X.; Xiong, P.; Xu, Y. Elucidation
of the Sodium-Storage Mechanism in Hard Carbons. Adv. Energy
Mater. 2018, 8, 1703217.
DOI: 10.1021/acsami.8b15274
ACS Appl. Mater. Interfaces 2018, 10, 41380−41388
ACS Applied Materials & Interfaces Research Article

(56) Ponrouch, A.; Marchante, E.; Courty, M.; Tarascon, J.-M.;

Palacín, M. R. In search of an Optimized Electrolyte for Na-ion
Batteries. Energy Environ. Sci. 2012, 5, 8572−8583.
(57) Ponrouch, A.; Dedryvère, R.; Monti, D.; Demet, A. E.; Mba, J.
M. A.; Croguennec, L.; Masquelier, C.; Johansson, P.; Palacín, M. R.
Towards High Energy Density Sodium Ion Batteries Through
Electrolyte Optimization. Energy Environ. Sci. 2013, 6, 2361−2369.
(58) Kim, H.; Hong, J.; Park, Y.-U.; Kim, J.; Hwang, I.; Kang, K.
Sodium Storage Behavior in Natural Graphite using Ether-based
Electrolyte Systems. Adv. Funct. Mater. 2015, 25, 534−541.
(59) Seh, Z. W.; Sun, J.; Sun, Y.; Cui, Y. A Highly Reversible Room-
Temperature Sodium Metal Anode. ACS Cent. Sci.ACS Central Science
2015, 1, 449−455.
(60) Lei, K.; Wang, C.; Liu, L.; Luo, Y.; Mu, C.; Li, F.; Chen, J. A
Porous Network of Bismuth Used as the Anode Material for High-
Energy-Density Potassium-Ion Batteries. Angew. Chem., Int. Ed. 2018,
57, 4687−4691.
(61) Xiao, L.; Cao, Y.; Henderson, W.; Sushko, M. L.; Shao, Y.;
Xiao, J.; Wang, W.; Engelhard, M. H.; Nie, Z.; Liu, J. Hard Carbon
Nanoparticles as High-capacity, High-stability Anodic Materials for
Na-ion Batteries. Nano Energy 2016, 19, 279−288.
(62) Chao, D.; Liang, P.; Chen, Z.; Bai, L.; Shen, H.; Liu, X.; Xia, X.;
Zhao, Y.; Savilov, S. V.; Lin, J.; Shen, Z. X. Pseudocapacitive Na-Ion
Storage Boosts High Rate and Areal Capacity of Self-Branched 2D
Layered Metal Chalcogenide Nanoarrays. ACS Nano 2016, 10,
10211−10219.

41388 DOI: 10.1021/acsami.8b15274

ACS Appl. Mater. Interfaces 2018, 10, 41380−41388