Carbon Resources Conversion 1 (2018) 104–108

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Carbon Resources Conversion

CHINESE ROOTS
GLOBAL IMPACT
j o u r n a l h o m e p a g e : www.keaipublishing.com/en/journals/carbon-resources-conversion/

Pyrolytic carbon derived from spent coffee grounds as anode for

sodium-ion batteries
Guoliang Gao a,b, Ling-Zhi Cheong c, Deyu Wang a, Cai Shen a,⇑
a
Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences, 1219 Zhongguan Road, Zhenhai District, Ningbo, Zhejiang, China
b
Guangzhou Key Laboratory for Special Fiber Photonic Devices, South China Normal University, Guangzhou 510006, China
c
School of Marine Science, Ningbo University, Ningbo 315211, China

a r t i c l e i n f o a b s t r a c t

Article history: This paper reported the facile preparation of pyrolytic carbon derived from spent coffee grounds and the
Received 27 February 2018 evaluation of its electrochemical performance when used as anode in sodium-ion battery. X-ray diffrac-
Revised 14 April 2018 tion analysis, scanning electron microscope, Brunauer–Emmett–Teller were employed to characterize the
Accepted 14 April 2018
structure of pyrolytic carbon. Electrochemical performances were tested by constant current charge–dis-
Available online 17 April 2018
charge, cyclic voltammetry and electrochemical impedance spectroscopy. Results showed that the pyro-
lytic carbon possess a porous structure (1–2 lm) and a specific surface area of 94.35 m2 g
1. When used
Keywords:
as anodes in sodium-ion batteries, a reversible capacity of 154.2 mA h g
1 at a current density of 200 mA
Spent coffee grounds
Sodium ion battery
g
1 after 50 cycles was obtained. Several electrolytes were evaluated and their electrochemical perfor-
Anode mances were compared. The result indicated that this material has excellent storage capacity and good
Pyrolytic carbon cycling stability. Our method provided a preparation of pyrolytic carbon from environmentally friendly
resources.
Ó 2018 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).

1. Introduction Na ion insertion and extraction resulting in rapid capacity fading in

Lithium-ion batteries (LIBs) have been widely used as working
power supplies for various electronic products because of their
large energy density, long cycle life, and small self-discharge
[1–6]. However, limited lithium resources, safety issue and poor
low-temperature performance have limited the large scale applica-
tions of LIBs. Thus, there is an urgent need to look for other storage
batteries to replace LIBs.
Sodium ion batteries (SIBs) appeared to be an attractive greener
alternative for LIBs. There are abundant sodium resources; and
sodium extraction technology from sea is already mature. In addi-
tion, both lithium and sodium belong to the same group of ele-
ments; and thus, sharing similar chemical properties [7–11].
Nevertheless, more work needs to be done to search for a suitable
anode material for use in SIBs. Conventional anode material that
has been used for LIBs are unsuitable for use in SIBs. For example,
graphite which has a capacity of 372 mA g
1 when used as anode
for LIBs demonstrated only 15 mA h g
1 in SIBs [12,13]. In addi-
tion, the lattice structure of graphite can be easily destroyed during
⇑ Corresponding author. Fax: +86 574 87910728.
E-mail address: shencai@nimte.ac.cn (C. Shen).
SIBs.
Hard carbon has been demonstrated to be good candidate as
anode material for SIBs. Table 1 shows the carbon source, fabrica-
tion process and electrochemical performance of the hard carbon
in previous studies. Dahn’s group has successfully prepared hard
carbon using glucose as precursor for the first time. A reversible
sodium capacity of 300 mA g
1 was achieved which is close to that
for lithium insertion in graphitic carbon anode [14]. Most of the
hard carbon currently investigated is derived directly or indirectly
from petrochemical or environmentally unfriendly resources. For
example, Yang et al. prepared carbon material derived from pitch
by oil-bath heating which showed an initial discharge and charge
capacity of 233.3 mA h g
1 and 79.2 mA h g
1, respectively [15].
Recently, there are an increasing number of researches on syn-
thesis of pyrolytic carbon from bio-resources such as coconut
shells [16], peanut shell [17], lignin [18], etc. In 2014, more than
9.1 million tons of coffee fruit were produced globally. Every kg
of instant coffee produces 0.9 kg of spent coffee grounds. Spent cof-
fee grounds which are relatively rich in carbon can be used as a
potential source for pyrolytic carbon and represent a kind of con-
centrated biomass resource. For example, Kim et al. reported that
carbon derived from waste coffee grounds can be used for methane
storage [19]; Xu et al. reported the conversion of coffee grounds

https://doi.org/10.1016/j.crcon.2018.04.001
2588-9133/Ó 2018 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 G. Gao et al. / Carbon Resources Conversion 1 (2018) 104–108
Table 1
Carbon source, fabrication process and electrochemical performance of pyrolytic carbons.
Carbon source Fabrication process
Spent coffee ground (C700) Simple sintering method
Natural graphite
Polystyrene cups Moderate temperature and high
pressure fabrication process in a sealed reactor
Sucrose Microwave-assisted reaction
Coal tar pitch Pyrolysis condensation method
Mesitylene (C9H12) Controlled thermal decomposition
Commercial hard carbon
Reduced graphene oxide (RGO)
Hollow carbon nanowires (HCNWs)
(a) (d)
(b) (c)
Sintering
Fig. 1. Schematic illustration of pyrolytic carbon derived from spent coffee grounds
as anode for batteries. (a) Coffee bean; (b) spent coffee grounds; (c) pyrolytic
carbon; (d) batteries.
into middle-caloric product gas [20,21]; Park et al. reported the
fabrication of supercapacitors by nanoporous carbonaceous
materials that obtained from coffee grounds [22]; Jang et al.
demonstrated the possibility of direct power generation from
waste coffee grounds via a high-temperature carbon fuel cell tech-
nology [23]. However, to the best of our knowledge, researches
about pyrolytic carbon derived from coffee grounds as anode mate-
rials for SIBs are rarely reported. Therefore, present study aims to
investigate the possibilities of synthesizing pyrolytic carbon from
spent coffee ground for use as anode materials in SIBs. Develop-
ment of anode materials from coffee grounds will reduce the cost
of SIBs and add value to spent coffee grounds. In this work, pyroly-
tic carbon was derived from spent coffee grounds by sintering pro-
cess at elevated temperature (Fig. 1). The morphology of the as-
prepared pyrolytic carbon was characterized by X-ray diffraction
analysis (XRD), scanning electron microscope (SEM), specific sur-
face area and porosity analysis. The pyrolytic carbon was then used
as active material of anode in SIBs. Battery performance was ana-
lyzed using constant current charge–discharge test, cyclic voltam-
metry and AC impedance test.
2. Experiment section
2.1. Preparation of pyrolytic carbon
Spent coffee grounds were put into beaker and washed several
times with deionized water to clean and adequately remove float-
ing and water soluble impurities in raw materials. Spent coffee
grounds were then filtered and transferred into Teflon-lined stain-
less autoclave at 150 °C for 2 h. Following that, the spent coffee
105
Capacity retention References

1
1
154.2 mA h g after 50 cycles at 200 mA g Present study
– 100 mA h g
1 after 500 cycles at 200 mA g
1 [12]
(Ether-based Electrolyte Systems)
– 15 mA h g
1 for the 3rd cycle at 200 mA g
1
(Carbonate-based Electrolytes Systems)
116 mA h g
1 after 80 cycles at 20 mA g
1 [25]
183 mA h g
1 after 50 cycles at 30 mA g
1 [26]
133 mA h g
1 after 200 cycles at 100 mA g
1 [27]
92 mA h g
1 after 50 cycles at 150 mA g
1 [28]
75 mA h g
1 after 50 cycles at 150 mA g
1 [28]
93.3 mA h g
1 after 250 cycles at 200 mA g
1 [29]
206.3 mA h g
1 after 400 cycles at 50 mA g
1 [30]
grounds were soaked in sodium carbonate solution (1 g L
1) for
more than 6 h to neutralize the remaining oil in the material. The
obtained materials were washed with deionized water and dried
in a drying oven. Finally, pyrolytic carbons were obtained by heat-
ing the obtained materials at a heating rate of 10 °C min
1 to 600,
700, 800, and 900 °C under flowing argon for 1 h. The four samples
obtained at 600, 700, 800, and 900 °C were denoted as C600, C700,
C800, C900, respectively.
2.2. Characterization of pyrolytic carbon
The obtained pyrolytic carbon were characterized by X-ray
diffraction (XRD, D8 Discover, Broker AXS, Cu radiation, k = l.5405
96 Å), scanning electron microscopy (SEM, S-4800, Hitachi).
Brunauer–Emmett–Teller (BET, Micromeritics, ASAP 2020M) and
X-ray Photoelectron Spectroscope (XPS, AXIS ULTRA DLD).
2.3 Electrochemical measurement
Electrodes were prepared by mixing active material, conductive
agent (super-p) and adhesive (PVDF) at a mass ratio of 7:2:1. N-
methyl pyrrolidone (NMP) was chosen as dispersant and the
obtained slurry was spread on copper foil. Metallic sodium was
used as counter and reference electrode. Three different elec-
trolytes were used namely 1 M NaClO4 solution in tetraethylene
glycol dimethyl ether (TEGDME), ethylene carbonate: dimethyl
carbonate (EC:DMC) (1:1 w/w) and EC:DMC (1:1 w/w) + 20 wt%
of fluoroethylene carbonate (FEC) with NaClO4 as conductive salt.
Glass fiber was used as separator. Coin cells (CR 2032) were assem-
bled in a glove box filled with argon. During the assembling oper-
ation, the moisture and oxygen levels were both kept below 0.1
ppm. Constant current charge and discharge test was conducted
in battery testing system within a voltage range of 0.01–3.00 V.
Cyclic voltammetry (CV) measurement and electrochemical impe-
dance spectroscopy (EIS) were performed on an electrochemical
workstation (Ametek 1470E) at a frequency range from 1 MHz to
10 mHz. CV measurement was conducted at a scan rate of 0.05
mV s
1.
3. Results and discussion
3.1. Structural and morphological characterization of the pyrolytic
carbon
Fig. 2 shows the XRD pattern of C700. Two typical characteristic
peaks of hard carbon can be observed at approximately 26° and
43°, which corresponds to the (0 0 2) and (1 0 0) crystal planes of
hard carbon. The intensive characteristic peak obtained at 26° indi-
cates parallel accumulation of graphite sheets. The weak peak at
106
(002)
Intensity (a.u.)
10 20
2 theta (deg.)
Fig. 2. XRD pattern of C700.
43° demonstrates the obtained product existed in the form of hon-
eycomb structures formed by sp2 hybridized carbons [16,17,24].
The Barrett–Joyner–Halenda (BJH) pore size distribution curve of
the porous carbon is shown in Fig. 3a. The as-prepared pyrolytic
carbon possessed narrow pore size distribution (100–300 Å).
According to the N2 adsorption–desorption test, surface area of
the carbon material is 94.35 m2 g
1. SEM micrographs (Fig. 3b) of
the pyrolytic carbon (1–2 lm) showed formation of void structure
which is mainly due to aromatization and carbonization of carbon
skeleton.
3.2. Electrochemical characterization
Fig. 4 shows the electrochemical performance of C600, C700,
C800 and C900 samples. Current density of the first two laps is
50 mA g
1, which increased to approximately 200 mA g
1 with
the aim to fully activate the battery at a low current in first two
cycles. It can be observed that a stable capacity is obtained after
activation during the first two cycles at a low current density of
50 mA g
1. No capacity fade was observed after 50 cycles demon-
strated the stability of the pyrolytic carbons. C700 showed the
highest reversible capacity of 154.2 mA h g
1; with about 91.7%
of the capacity was maintained at a current density of 200 mA
g
1 after 50 cycles. The capacity of C700 tested in present study
(a) 0.00012
0.00010
0.00008
dV/dD(cm g )
3 -1
0.00006
0.00004
0.00002
0.00000
0 200
G. Gao et al. / Carbon Resources Conversion 1 (2018) 104–108
400
600 °C
Specific capacity (mAh g )
700 °C
-1
300 800 °C
900 °C
200
(100)
100
0
0 10 20 30 40 50
30 40 50
Cycle number (n)
Fig. 4. Cycling performances of C600, C700, C800 and C900.
was higher or comparable with previously published data obtained
from pyrolytic carbons [12,25–30] (Table 1).
Sintering temperature of the pyrolytic carbon was found to
have insignificant effect on the cycle stability of the electrode
materials, but it demonstrated a large effect on the sodium storage
capacity. According to ‘‘falling cards model”, high sintering tem-
perature will result in destruction of the small pore size structure
which will be replaced by formation of large pore size structure.
Large pore structures were found to reduce the amount of inserted
sodium ions, which decreased the capacity [31].
Fig. 5a shows the charge and discharge curves of sample C700
measured in TEGDME-based electrolyte. The curves revealed typi-
cal characteristics of hard carbon as anode materials for sodium
batteries, namely a slope area in a region of high voltage (0.1–1
V) and a flat area in low voltage (0–0.1 V). There is a mild polariza-
tion phenomenon in the slope area as the number of loops goes up.
The first charge and discharge capacity of the materials were 198.9
mA h g
1 and 362.6 mA h g
1, respectively, which corresponded to
a coulombic efficiency of 54.9%. Capacity loss of C700 was mainly
due to formation of SEI layer, which consumed a large amount of
sodium ions. In addition, the porous surface structure of C700
can easily absorb moisture and oxygen, which reacted with sodium
ion and increased the irreversible capacity [12]. In the second
cycle, the coulombic efficiency increased to 87.1%. The curves for
10th and 50th cycles were coincidence with the 5th cycle curve,
demonstrating good stability of the pyrolytic carbons.
(b)
400 600 800 1000 1200
Pore diameter (Å)
Fig. 3. BJH pore size distribution curve (a) and SEM image (b) of C700.
 G. Gao et al. / Carbon Resources Conversion 1 (2018) 104–108 107

3.0
(a) 1 st cycle (b)0.05
2.5 2 nd cycle
5 th cycle

Voltage (V vs. Na/Na )

+
10 th cycle
2.0 50 th cycle

Current (mA)
0.00

1.5
1 st cycle
2 nd cycle
3 rd cycle
1.0 -0.05
4 th cycle
5 th cycle
0.5

-0.10
0.0
0 50 100 150 200 250 300 350 400 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-1 +
Specific capacity (mAh g ) Voltage (V vs. Na/Na )

(c)400 (d)
500

350
before cycling
400
Specific capacity (mAh g )
-1

10 th cycle
300 50 th cycle

250 300

-Z'' (ohm)
-1
50 mA g -1
50 mA g
200 -1
100 mA g 100 mA g
-1

150 200 mA g
-1
-1
200 mA g
200
-1
500 mA g
100
100
50

0 0
0 10 20 30 40 50 60 70 0 200 400 600 800 1000
Cycle number (n) Z' (ohm)

Fig. 5. Electrochemical performance of C700 electrode: (a) galvanostatic discharge–charge curves measured at current density of 200 mA g
1 between 0.01 and 3 V (vs. Na/
Na+); (b) cycling voltammetry (CV) curves of the initial 5 cycles at a scanning rate of 0.05 mV s
1; (c) rate capability at different current density from 50 mA g
1 to 500 mA
g
1; (d) Nyquist plots of the electrode before cycling, after 10 and 50 charge–discharge cycles at 200 mA g
1.

CV curves of the C700 were recorded for the first five cycles in a back to 50 mA g
1, the capacity can go back to 190 mA h g
1,
potential window of 0.01–3.0 V (vs. Na/Na+) at a scanning rate of demonstrating excellent rate performance.
0.05 mV s
1 (Fig. 5b). There are two obvious irreversible reduction Fig. 5d shows the EIS of the C700. The depressed semicircle
peaks at around 0.6 and 0.9 V in the first cycle. The two peaks can located in the high frequency area represents formation of SEI film
be attributed to formation of SEI and decomposition of electrolyte. and charge-transfer impedance. A straight line at the low fre-
The reversible reduction and oxidation peaks at around 0 V and 0.1 quency corresponded to sodium ion diffusion inactive material
V can be ascribed to Na-ion insertion–extraction in the interlayers [32]. After the 10th cycle, EIS of the C700 significantly reduced.
of the hard carbon. A high degree of similarity existed in CV curves In the meantime, the resistance decreased slightly after 50th cycle.
during the 2nd to 5th cycle, illustrating good reversibility of The findings showed a good reaction kinetics and a stable surface
sodium ion intercalation and deintercalation on electrodes, which of electrodes during charging and discharging process.
is consistent with the aforementioned finding on charge and dis- Fig. 6 shows electrochemical performance of C700 electrode
charge curves. cycled in several common electrolytes. A higher discharge capacity
Fig. 5c shows the rate capability of C700 evaluated at different and smaller coulombic efficiency can be observed when 20% FEC
current densities. When the current density is 50 mA g
1, the dis- electrolyte was used in comparison to EC: DMC mixtures (without
charge capacity remained at 195 mA h g
1. The capacity demon- any additive) for the first cycle (Fig. 6a). There is a serious prema-
strated a descending trend with increased current density. As the ture capacity loss in 20% FEC added electrolyte. This is probably
current density increased to 500 mA g
1, the discharge capacity due to thin and scattered SEI film formed by EC/DMC electrolyte,
was stable at around 115 mA h g
1. As the current density went meanwhile SEI film formed by 20% FEC added electrolyte is uni-

Fig. 6. Electrochemical performance of C700 in several common electrolytes: (a) galvanostatic discharge–charge curves measured between 0.01 and 3 V (vs. Na/Na+); (b)
cycling performance and coulombic efficiency at a current density of 200 mA g
1.
108 G. Gao et al. / Carbon Resources Conversion 1 (2018) 104–108
form and compact [33]. The latter can increase the impedance of
batteries [34], and reduced the specific capacity. SEI layer has been
shown to slow down formation of sodium dendrite to some extent
which will increase cell cycling stability. This is confirmed by good
coulombic efficiency when FEC-added electrolyte was used. Fig. 6b
shows ether-based electrolyte (TEGDME electrolyte) possessed the
highest capability. TEGDME electrolyte can form stable Na+-solvent
complexes because of its high donor number [13]. In addition,
TEGDME electrolyte was known to forming a trivial SEI film on
the surface of hard carbon making it easier for Na+-solvent to
spread into the crystal lattice of hard carbon. As a result, its specific
capacity is higher than that of carbonate-based electrolytes [13].
4. Conclusion
Pyrolytic carbon was prepared by a simple sintering method
from spent coffee grounds. When it was used as electrode materi-
als for sodium-ion batteries, a reversible capacity of 154.2 mA h g

1
was obtained at a current density of 200 mA g
1, indicating
the as-prepared pyrolytic carbon has significant sodium storage
capacity. By comparing its electrochemical performances in several
common electrolytes, it can be concluded that co-intercalation
phenomenon of ether-based electrolyte make it more suitable than
carbonate-based electrolytes as cycling electrolyte when hard car-
bon was used as anode materials in SIBs.
Acknowledgements
We thank the National Key Research and Development Program
(Grant No. 2016YFB0100106) and the Youth Innovation Promotion
Association, Chinese Academy of Sciences (2015239) for financial
supports.
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