Carbon 144 (2019) 582e590

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Melamine assisted liquid exfoliation approach for the synthesis of

nitrogen doped graphene-like carbon nano sheets from bio-waste
bagasse material and its application towards high areal density Li-S
batteries
Dasari Bosu Babu a, b, Kannadka Ramesha a, b, *
a
CSIR-Central Electrochemical Research Institute-Chennai Unit, CSIR-Madras Complex, Taramani, Chennai, 600113, India
b
Academy of Scientific and Innovative Research (AcSIR), CSIR-CECRI, Karaikudi, 630003, India

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

Article history: Li-S battery has received considerable attention as futuristic technology, however, solutions for chal-
Received 27 October 2018 lenging problems such as polysulfide shuttle and low sulfur loadings, etc. still remain elusive. Here we
Received in revised form report design of efficient polysulfide trap by preparing graphene like nitrogen doped carbon (NBC) sheets
20 December 2018
from bagasse (sugarcane waste). Further, we prepared S@NBC composites by chemical absorption of S
Accepted 28 December 2018
Available online 28 December 2018
onto NBC matrix and studied their beneficial aspects as cathode for Li-S battery. The S@NBC displays
extraordinarily good performance with a reversible capacity of 1169 mAh g
1 at 0.2 C with 77% capacity
retention after 200 cycles which also exhibits remarkable 85% retention of higher order polysulfide even
Keywords:
Li-S battery
after 200 cycles. Moreover, by placing a second cathode layer the cyclability will be increased beyond 500
Nitrogen doped carbon cycles. The remarkable cycling performance is attributed to the effective chemisorption of sulfur and
Bagasse polysulfides by the nitrogen doped carbon. Further, sulfur loading is increased to 12 mg cm
2 by stacking
Graphene like carbon sheets four cathode layers and we could achieve high areal capacity of 12 mAh cm
2 which is three times higher
High energy density than the present day lithium ion battery.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Considering the environmental impacts and depletion of fossil
fuels, the electrochemical energy storage devices such as lithium
ion batteries are being considered as promising alternatives due to
their high energy density and long cycle life [1]. But, the energy
density of present day lithium-ion technology is limited by the
‘intercalation chemistry’ of electrode materials (387 Wh kg
1 for
LiCoO2/graphite) [2]. In this scenario Li-S battery draw huge inter-
est due to the conversion reaction of sulfur, i.e. S8 þ 16 Li þ þ16e-
/ 8Li2S with two electron transfer for each sulfur atom. This leads
to high theoretical capacity of 1675 mAh g
1 and an average voltage
of 2.2 V V Li/Liþ. Hence Li-S system can offer energy density
2567 Wh kg
1, which is 3e4 times of present lithium-ion battery
[3,4]. On the other side, the insulating nature of sulfur and the
* Corresponding author. CSIR-Central Electrochemical Research Institute-Chennai
Unit, CSIR-Madras Complex, Taramani, Chennai, 600113, India.
E-mail address: ramesha.cecri@gmail.com (K. Ramesha).
polysulfide “shuttle effect “ are the determining factors in the cell
performance [5]. Moreover, the continuous charge-discharge pro-
cess involves repeated volume change (80%), that can results in
pulverization of sulfur cathode [6]. To overcome these problems,
researchers are employing chemical modifications to cathode,
separator, electrolyte, and anode [7e11].
The most hampering issues like insulating nature sulfur and
polysulfide dissolution can be solved by employing conductive
porous carbon as sulfur host, which can increase the conductivity of
sulfur as well as encapsulate polysulfides in the porous architecture
[12,13]. However, the non-polar nature of the carbon displays low
binding towards polysulfide, leading to detachment of the product
(Li2S) from the electrode resulting in loss of electrical contact and
capacity degradation [14]. Hence, heteroatom (Nitrogen, Sulfur,
Phosphorus, Oxygen, and Boron) doping in carbon matrix plays a
significant role in enhancing polysulfide capture and improving cell
performance [15e18]. Precisely, the nitrogen doping has distinct
importance because it offers more active sites for ion absorption
and improves the electrochemical activity in addition to enhancing
the electronic conductivity and wettability of the carbon

https://doi.org/10.1016/j.carbon.2018.12.101
0008-6223/© 2019 Elsevier Ltd. All rights reserved.
 D.B. Babu, K. Ramesha / Carbon 144 (2019) 582e590
[17,19e22]. Nitrogen doping has been reported for CNTs, graphene
and porous carbons [23e25]. Graphene has been explored widely
in Lithium - sulfur battery applications due to its remarkable high
electronic, thermal and mechanical properties [26,27]. But, the
synthesis of graphene needs expensive raw materials and involve
hazardous synthesis techniques [28]. These factors limit the wide
utilization of graphene. Hence the synthesis of graphene from the
bio-waste materials is highly promising for large-scale applications
due to cost-effective process and abundant raw material availabil-
ity. In this direction, graphene synthesis from bio-waste materials
like peanuts, rice husk, and disposal paper cups etc. has been re-
ported [29e32].
Bagasse (fibrous dry matter of sugar cane) is widely available as
bio waste. Annually about 54 million dry tons of bagasse is pro-
duced worldwide as residue after the extraction of sugar from sugar
cane [33]. Considering the abundance of availability we have
investigated conversion of the bio-waste into nitrogen-doped gra-
phene-like carbon adopting a simple hydrothermal synthesis and
using melamine as nitrogen source. Interestingly, the amount of
melamine used during synthesis plays important role in the for-
mation of graphene like carbon sheets. For the best our knowledge,
this is the first report on use of nitrogen doped bagasse derived
carbon for the Lithium-sulfur battery applications. When pristine
carbon derived from bagasse was used for making cathode com-
posite, the Li-S cell shows 821 mAh g
1 capacity, while the nitrogen
doping onto this carbon enhances the reversible capacity to 1169
mAh g
1 at 0.2 C rate. Also an excellent rate capacity of 454 mAh
g
1 at 4 C rate and long-term cycling stability with good capacity
retention up to 500 cycles was observed. We also achieved sulfur
loading up to 12 mg cm
2 with the exceptional high areal capacity
of 12 mAh cm
2 which is 3 times higher than commercial lithium
ion battery.
2. Experimental section
2.1. Material preparation
2.1.1. Nitrogen doped carbon preparation
Nitrogen (N) doped carbon sheets were prepared from bagasse
derived carbon and melamine as follows. Sugarcane bagasse, a
waste residue after juice extraction is received from local sugar
cane shop. A small quantity of this residue was dried at room
temperature for 48 h. The dried cane pitch was crushed into small
pieces and mixed with melamine at various weight ratios of
bagasse to melamine 1:0, 1:5, 1:10, 1:15 and 1:20 in Teflon lined
autoclave. 25 ml of distilled water was added to the autoclave (50%
filling) and was maintained at 180  C for 10 h during hydrothermal
synthesis followed by cooling to room temperature. The black color
product formed was filtered to remove excess amount of melamine,
washed with distilled water several times and dried in an oven at
70  C overnight. Further, the obtained product was heated at 850  C
for 3 h under argon atmosphere to obtain N-doped graphene like
carbon sheets. The product was washed with 0.1M ammonium di
hydrogen fluoride and oven dried. Based on the weight ratio of
melamine used during the synthesis the products are labelled as,
pristine bagasse carbon (BC), and N-doped carbons as NBC-5, NBC-
10, NBC-15 and NBC-20.
S@NBC preparation: 70 mg sulfur powder was sonicated for
30 min in 50 ml DMF solvent until yellow color sulfur dissolves.
About 30 mg of NBC was added to the above solution and again
sonicated for 30 min. The solution mixture was transformed to
beaker containing 1000 ml de-ionized water, immediately the so-
lution changes from colorless to white indicating colloidal sulfur
formation. The solution was further stirred for 4 h until the white
color disappears and the solution changes to colorless which
583
ratifies that all sulfur is absorbed on the pores and surface of NBC.
This S@NBC composite was filtered and dried overnight at 65  C.
The XRD of sulfur powder, NBC-15 and composite S@NBC-15 are
compared in Figure S1 which confirms the presence of sulfur on the
surface of NBC-15.
2.2. Electrochemical measurements
S@NBC composite is mixed with 10% SP carbon and 10% PVDF
binder and made into slurry using NMP as solvent. The slurry is
coated on to CNT paper and used as cathode (the sulfur loading
3.2 mg cm
2). Lithium metal (foil thickness 700 mm) acts as both
reference and counter electrode. Celgard (2400) is used as the
separator. The electrolyte is 1 M bis (trifluoromethane) sulfonamide
lithium salt (LiTFSI, Sigma-Aldrich) in 1, 2-dimethoxyethane (DME,
Sigma-Aldrich) and 1, 3 Dioxalane (DOL, Sigma-Aldrich) in 1:1 V/V%
with 0.25 M LiNO3 additive. Coin cells were assembled in argon
filled glove box (where O2, H2O levels restricted to 1 ppm). The
cells were galvanostatically cycled in the voltage range of 1.7e2.7 V.
All experiments are carried out in VMP3Z Biologic multichannel
galvanostat/potentiostat. The cycling voltammetry is performed at
0.01 mV scan speed within the potential range of 1.7e2.7 V and
electrochemical impedance studies were performed over a fre-
quency range of 400 kHz to 50 mHz. The capacities are calculated
based on mass of sulfur in the electrode.
3. Results and discussions
3.1. Structural analysis
Fig. 1a shows the XRD of BC, NBC-5, NBC-10, NBC-15 and NBC-20
respectively. All the XRD patterns show two broad diffraction peaks
corresponding to (002) and (100) planes of the hexagonal graphitic
carbon. The structure and quality of the carbon materials are
characterized using Raman spectroscopy. The Raman spectrum of
BC, NBC-5, NBC-10, NBC-15 and NBC-20 respectively are shown in
Fig. 1b. All spectra show peaks at 1585 cm
1 and 1343 cm
1 which
represents G and D bands of carbon.
The G band is due to the E2g stretching mode of graphite,
assigned to the presence of sp2 carbon and the intensity provides
the information about the degree of graphitization [34]. The D band
(A1g symmetry) represents structural disorder in the sp2 carbon
[17]. Hence, the disorder of the carbon can be quantified by the ID/IG
ratio. The ID/IG ratio for BC, NBC-5, NBC-10, NBC-15 and NBC-20
samples are 1.02, 1.06, 1.07, 1.085 and 1.15 respectively. The in-
crease in the ID/IG ratio indicates significant increase in number of
defective sites that can be attributed to increased nitrogen doping.
Along with G and D band, a small 2D band (at 2750 cm
1) which is
characteristics of graphene is also observed for NBC-10, NBC-15 and
NBC-20 [35,36]. This 2D band is absent for pristine (BC) and NBC-5
samples indicating that melamine quantity is playing a crucial role
in exfoliation of graphitic carbon into graphene-like sheets.
The XPS analysis is carried out to investigate functionality of
nitrogen present in the sample. Fig. 1C shows nitrogen spectra for
NBC-10, NBC-15 and NBC-20. The spectra can be deconvoluted into
3 peaks corresponding to pyridinic, pyrrolic and graphitic nitrogen.
The pyridinic, pyrrolic groups generate polarity to the carbon ma-
trix which will enhance polysulfide absorption as discussed later
[37]. The graphitic nitrogen helps in increasing the electronic
conductivity of the carbon [38]. Additionally, by using area under
the curve the amount of pyridinic, pyrrolic and graphitic nitrogen
present in the compound is calculated and it is given in table S1. In
three samples compared to pyridinic, pyrrolic nitrogen, graphitic
nitrogen having higher percentage indicates good conductivity of
carbon. By using CHNS analyzer, the amount of nitrogen present in
584 D.B. Babu, K. Ramesha / Carbon 144 (2019) 582e590

Fig. 1. (a) XRD and (b) Raman spectra of BC, NBC-5, NBC-10, NBC-15 and NBC-20 carbon samples (c) XPS spectra of NBC-10, NBC-15 and NBC-20 (d) percentage of various nitrogen
groups present in the total nitrogen content for NBC-10, NBC-15 and NBC-20. (A colour version of this figure can be viewed online.)

the NBC-5, NBC-10, NBC-15 and NBC-20 sample is evaluated which
is tabulated in Table S2. The nitrogen content in the carbon samples
is proportional to the melamine weight ratio used during synthesis.
The comparison of total nitrogen and the presence of different ni-
trogen's in the samples is shown in Fig. 1d.
Fig. 2 shows SEM images of pristine (BC) and N-doped carbon
samples. Fig. 2(a and b) displays the pristine carbon (BC) having
tube like morphology with 1e2 mm wall thickness. Few carbon
spheres ranging 50e200 nm are also seen in Fig. 2b (inset) which is
attributed to conversion of leftover sucrose in the bagasse into
carbon spheres during the hydrothermal process. Fig. 2 c is the SEM
of NBC-5 showing peeling off of thin carbon sheets on the surface of
carbon tubes. When the melamine percentage increases to 10 or
above (NBC-10, NBC-15) the rate of exfoliation increases and gra-
phene like carbon sheets are observed (Fig. 2deg). Fig. 2g shows
graphene like layered carbon sheets. Interestingly, carbon sheets

Fig. 2. SEM images of (a, b) pristine, (c) NBC-5, (d, e) NBC-10, (f, g) NBC-15, (h) NBC-20.
 D.B. Babu, K. Ramesha / Carbon 144 (2019) 582e590
are found to be decorated with carbon spheres (Fig. 2e). However,
when the melamine content is increasing it is observed that the
percentage of spheres decreased which may be due to the con-
version of carbon spheres also into sheets. Finally, when the mel-
amine ratio further increases to 20 (Fig. 2 h) exfoliated graphene
like sheets found to be damaged which might be due to the high
amount of nitrogen present in the carbon matrix.
The SEM image and elemental mapping of NBC-15 is displayed
in Fig. 3(a and b) which shows nitrogen doped graphene like
structure with uniform distribution of nitrogen throughout the
carbon sheet. HRTEM images of NBC-15 (Fig. 3c and d) confirm
formation of carbon sheets and in addition, carbon spheres can also
be seen. HRTEM images of NBC-20 shown in Fig. 3e and f where the
carbon sheets are slightly damaged as shown by circled area.
3.2. Possible mechanism for the formation graphene-like carbon
from bagasse
Bagasse consists of cellulose, hemi cellulose and lignin as major
organic compounds and these are rich in hydroxyl group. This
functional groups can easily attract water molecules by hydrogen
bonding, as a result water can easily spreads uniformly throughout
bagasse. In hydrothermal conditions melamine can dissolve in hot
water, hence melamine can easily intercalate into the structure
with the help of water. Due to the intercalation (absorption) of
melamine and water, bagasse fibers get laterally expanded and
appear yellowish in color (otherwise black when melamine is not
present) (Fig. 4b). Around 350  C, melamine melts and interacts
with graphite sheet through p-p interactions [39]. Recent DFT
calculations show that triazine groups (in melamine) have strong
affinity to absorb on graphitic carbon [40,41]. This molecular ab-
sorption results 2D molecular assembly in graphite structure [42].
Above the melting point, melamine distributes uniformly within
the carbon matrix thereby effectively compensating the van der
waals force between the sheets [43]. When the temperature in-
creases to 600  C, the polycondensation of melamine results in the
formation of carbon nitride [44]. The XRD of the sample heated at
600  C confirms the presence of g-C3N4 (Fig. S2), when the tem-
perature further increase to 850  C these chemical processes will
eventually lead to exfoliation of carbon structure into sheets con-
taining 4e8 layer graphene as shown in AFM (Fig.S3). Concomi-
tantly, nitrogen groups from decomposed carbon nitride get
attached to the active sites of the carbon to form nitrogen doped
Fig. 3. (a,b) SEM image and corresponding elemental mapping for nitrogen of NBC-15.
HRTEM images of (c, d) NBC-15 (e, f) NBC-20. (A colour version of this figure can be
viewed online.)
585
carbon [45,46]. As the amount of melamine increases exfoliation
rate also increases yielding product with high surface area and
higher nitrogen content. XRD, IR spectra confirms the absence of
graphitic nitride (Fig S2 & Fig S4) and Raman, AFM, TEM and
elemental analyses confirm nitrogen doped graphene like structure
(Figs. 1 and 3& Fig S3). It is also to be noted that hydrothermal
treatment is an essential step in order to get graphene like struc-
tures, direct heating of melamine and bagasse (without hydro-
thermal treatment) at 850  C resulted in tube like structures as seen
by FESEM with most of region showing broken or pulverized tubes
(Fig. S5).
3.3. Investigation of N-doped carbon sheets derived from bagasse as
sulfur host for Li-S batteries
Considering the high surface area and graphene like
morphology we presumed that NBC may be suitable as S host in Li-
S batteries. Besides, the nitrogen doping can impart high polarity to
carbon scaffold which is useful in binding polysulfides and can
effectively reduce the shuttle phenomenon. For this NBC-S com-
posites (S@NBC) were prepared and used as cathode in Li-S battery.
The electrochemical performance of the cells were investigated in
detail as described below.
3.4. Electrochemical cyclic voltammetry
The Cyclic Voltammetry (CV) of S@BC, S@NBC-10, S@NBC-15
and S@NBC-20 Vs Li in the voltage range of 1.7e2.7 V are shown in
Fig. 5a-d. The CV data shows that the reduction of the sulfur takes
place in two steps, in the initial cathodic scan the reduction peak at
2.4 V is related to conversion of sulfur to higher order lithium
polysulfides Li2Sn (4  n  8). The second reduction peak observed
at 2.1 V is related to conversion of higher order polysulfides to the
final reduction product Li2S2/Li2S. Similarly, during anodic scan
oxidation takes place in two step process, one at 2.35 V which is
conversion of Li2S2/Li2S to polysulfide and the second is at 2.42 V
which is conversion of polysulfide to elemental sulfur. Due to the
poor conductivity and week polysulfide absorption capability, the
area under CV is smaller for pristine carbon (S@BC). Further, peak
intensities are decreasing with cycle number indicating the poly-
sulfide dissolution [47]. Where as in case of S@NBC-10, S@NBC-15
and S@NBC-20, the peaks are relatively sharp and superimpose for
several cycles indicating less polarization, good polysulfide reten-
tion and cycling stability. Comparison of initial CV curves of S@BC,
S@NBC-10, S@NBC-15 and S@NBC-20 are shown in Fig. S6. The CV
reveals the positive effect of N doping into the carbon matrix which
improves conductivity and polysulfide retention ability.
3.5. Discharge- charge analysis
The comparison of corresponding initial cycle of the charge -
discharge data of S@BC, S@NBC-10, S@NBC-15 and S@NBC-20
respectively at 0.2 C rate are shown in Fig. 6a. The corresponding
first 5 cycle charge-discharge plots are shown in Fig. S7. The gal-
vanostatic discharge plots show two plateaus (at 2.4 V and 2.1 V)
similar to CV data. The small plateau at 2.4e2.1 V range in the
discharge data corresponds to the conversion of elemental sulfur S8
to higher order polysulfides i.e., Li2Sn (where 4  n  8). The long
discharge plateau (at 2.1 V) is due to the conversion of higher order
polysulfide to lower order sulfides Li2S2/Li2S. Similar to discharge,
the charging also consists two plateau regions, one upper plateau at
2.2 V corresponds to the conversion of Li2S/Li2S2 to higher order
polysulfides and the other small plateau at 2.35 V is due to the
oxidation of polysulfides to elemental sulfur. The potential differ-
ence (DE) between discharge (at 2.1 V) and charge is calculated for
586 D.B. Babu, K. Ramesha / Carbon 144 (2019) 582e590

Fig. 4. (a) Schematic mechanism of nitrogen doped graphene like carbon sheets from sugarcane waste. (b) Color variations of bagasse after hydrothermal process, bagasse:
melamine is 1:0, 1:10 and 1:20. (A colour version of this figure can be viewed online.)

Fig. 5. (a-d) Cyclic voltammetamogram of S@BC, S@ NBC-10, S@NBC-15 and S@NBC-20. (A colour version of this figure can be viewed online.)

the initial 100 cycles of S@BC, S@NBC-10, S@NBC-15 and S@NBC-20 all, lowest DE is observed for S@NBC-15. Further, the impedance of
respectively (Fig. 6b). In the case of nitrogen doped carbon the the fresh cells (for S@BC, S@NBC-10, S@NBC-15 and S@NBC-20) are
polarization decreases which indicate nitrogen doping effectivity plotted in Fig. 6c. The decrease in charge transfer resistances of the
enhance the electronic properties sulfur-carbon composite. Among nitrogen doped carbon samples with respect to the pristine
 D.B. Babu, K. Ramesha / Carbon 144 (2019) 582e590
Fig. 6. Comparison of S@BC, S@NBC-5, S@NBC-10, S@NBC-15 and S@NBC-20 samples (a) initial cycles charge curves (b) The average potential Vs cycle number (c) EIS of fresh cell (d)
Higher order polysulfide capacity Vs Cycle number. (A colour version of this figure can be viewed online.)
suggests increase in conductivity upon N-doping. Also, charge
transfer resistance decreases with the increase in nitrogen per-
centage in the samples.
3.6. Polysulfide retention studies
During the galvanostatic discharge, we observe two plateaus;
one at 2.4 V (upper plateau) and another at 2.1 V (lower plateau).
Theoretical capacities of these plateau are 419 mAh g
1 (25%) and
1256 mAh g
1 (75%) respectively. The upper plateau corresponds to
polysulfide concentration and decrease in its length during cycling
indicates capacity loss in the battery due to the dissolution of
higher order polysulfides. It is highly important to control higher
order polysulfide dissolution for better cyclability. Due to the non-
polar nature, the pristine bagasse carbon cannot hold high amount
sulfur, resulting in poor cycling capacity and faster polysulfide
dissolution. It has been shown that chemical interaction between
the carbon host and polysulfide species will have better stability
than physical interactions [25,48]. The nitrogen doping will make
the carbon matrix positively charged that can increase the poly-
sulfide affinity. Introduction of nitrogen, renders a stable higher
order polysulfide capacity (Qhps) (Fig. 6a) which improves with
increase in N-doping. Fig. 6d show comparison of Qhps with
respect to cycle numbers for pristine and N-doped carbon samples
for 200 cycles. The initial Qhps for S@BC, S@NBC-10, S@NBC-15 and
S@NBC-20 are 280, 220, 318, 325 and 346 mAh g
1 respectively and
after 200 cycles the obtained Qhps values are 102, 155, 235, 275 and
250 mAh g
1 respectively. The higher order polysulfide capacity
retention (Qhps) can be calculated as (Qhps)final cycle/(Qhps)initial
cycle x 100. The Qhps retention for S@BC, S@NBC-10, S@NBC-15 and
S@NBC-20 are 36.5, 70.5, 74, 85 and 72% respectively. These values
indicate that the highest polysulfide capacity retentions is observed
587
for S@NBC-15 due to the optimized nitrogen percentage in the
carbon matrix.
3.7. Battery performance analysis
Fig. 7a shows comparison of Li-S battery cycling performance of
S@BC, S@NBC-10, S@NBC-15 and S@NBC-20 respectively at 0.2 C
rate up to 200 cycles. When compared to the pristine carbon, the N-
doped carbons show higher capacity retention and better
coulombic efficiency. At 0.2 C rate, the observed initial capacities of
S@BC, S@NBC-10, S@NBC-15 and S@NBC-20 respectively are 821,
890, 1001, 1169 and 1100 mAhg
1 and the final capacities are 347,
531, 672, 898 and 790 mAhg
1 respectively. The lower capacity of
S@BC sample is due to the nonpolar nature of carbon and poor
binding to polysulfides species formed during the electrochemical
reaction. The electron donating nitrogen species enhances the
conductivity of the carbon matrix which in turn improves sulfur
activity, leading to superior Li-S battery performance. Also, nitro-
gen acts as a Lewis base to interact with strong Lewis acids of ter-
minal Li atoms in lithium polysulfides (LiSn Liþ … N) through
dipole-dipole interactions [49,50]. Which can decrease the poly-
sulfide dissolution, restrict polysulfides to the cathode side and
thereby can impart improved cycling performance. Among all
compositions, S@NBC-15 exhibit higher cycling stability and less
polarization specifying the optimum nitrogen doping in the carbon
matrix. The corresponding elemental mappings of the Pristine and
after 200 cycles are shown in Fig. S8, S9 which shows sulfur is
distributed throughout the electrode which confirms redistribution
of polysulfides. The comparison of capacity retention of S@BC,
S@NBC-10, S@NBC-15 and S@NBC-20 are shown in Fig. 7b.
Comparative all S@NBC-15 shows good capacity retention 77% after
200 cycles at 0.2C. The rate capability of the S@NBC-15 carbon
588 D.B. Babu, K. Ramesha / Carbon 144 (2019) 582e590
Fig. 7. (a, b) Comparison of cycling performance and respective capacity retentions of S@BC, S@NBC-5, S@NBC-10, S@NBC-15 and S@NBC-20 at 0.2C. (A colour version of this figure
can be viewed online.)
along with the discharge - charge profile at different rates are
shown in Fig. 8(a and b). As seen, a high initial capacity of 1280 mAh
g
1 is achieved at 0.1 C rate which indicates 77% of sulfur utilization.
As the cycling rate varies from 0.1 C to 4 C, the battery delivers
capacities of 1127, 1120, 932, 722, 548, 454 mAh g
1 at 0.1, 0.2, 0.5, 1,
2, 3 and 4 C respectively, indicating excellent cell performance.
The high amount of sulfur loading is difficult with conventional
Li-S system and most of the cases it is limited to sulfur loadings
<2 mg cm
2. This low sulfur loading limits the energy density of Li-
S batteries. Though S@NBC-15 exhibits best performance, still the
maximum areal sulfur loading possible is 3.2 mg cm
2. For practical
applications it is necessary that the areal loading of sulfur
is > 6 mg cm
2 [6]. Though good stability is observed for
3.2 mg cm
2 sulfur loaded cathode, the areal density is less than
conventional lithium ion batteries. However, it is common in Li-S
batteries that higher sulfur loading causes serious polysulfide
dissolution. This inevitable polysulfide dissolution calls for various
engineering strategies to improve both sulfur loading (energy
density) and cyclability (capacity retention). To increase the areal
sulfur loading, we adopted the strategy of multiple cathode layer
stacking. The advantage of this approach is that the porous CNT
paper which is used as the positive current collector will also act as
a physical barrier to absorb the dissolved polysulfides from the
previous layer. Also the conductive nature of the CNT reactivates
the non-conductive reaction product (Li2S) which has agglomer-
ated on the electrode surface. This multiple cathode stacking
Fig. 8. (a,b) Charge-discharge profile of S@NBC-15 at various rate and corresponding capacities. (A colour version of this figure can be viewed online.)
strategy not only increases sulfur loading but also retards poly-
sulfide shuttle effect.
To evaluate the advantages of cathode stacking, Li-S cells con-
sisting two cathode layers were fabricated and their long term
cycling performance was evaluated (Fig. 9a). At 0.5 C rate, the cell
containing two cathode layers of S@NBC-15 showed an initial
discharge capacity of 1098 mAh g
1 while the cell with two cathode
layers of S@NBC-20 showed 1299 mAh g
1 capacity. After 500 cy-
cles the capacity obtained for the above mentioned cells are 682
and 563 mAh g
1. As shown in Fig. 9b, using two cathode layers in
the Li-S system, we could achieve higher areal capacity compared
to conventional Li-ion batteries. The initial areal capacity of S@NBC-
15, S@ NBC-20 are 6.8, 8 mAh cm
2 at 0.5 C rate. These capacities
are nearly double to the conventional lithium ion batteries. Further
we applied this layer by layer strategy to stack multiple layers of
S@NBC-15 to increase sulfur loading from 3.2 to 12 mg cm
2. With
2 layer, 3 layer and 4 layers, the initial areal densities obtained are
8.5, 11, 12 mAh cm
2 whereas the areal density of conventional
lithium ion batteries is around 4 mAh cm
2.
The comparison of present work with previous reported litera-
ture of bio-derived materials is shown in Fig. 9d the corresponding
references and cycling data is shown as numbers which are given in
supporting information Table S3. It can be recognized that present
work reports improved performance in terms of sulfur loading,
capacity retention and cycle life.
 D.B. Babu, K. Ramesha / Carbon 144 (2019) 582e590
Fig. 9. (a, b) long cycling performance of S@NBC-15 and S@NBC-20 and respective areal capacities (c) Areal capacities of S@NBC-15 with various sulfur loading (d) Comparison of
capacity retention data of the present work with literature reports. The reference numbers cited here are listed in the supplementary information. The numbers in the bracket
indicate sulfur loadings in mg cm
2. (A colour version of this figure can be viewed online.)
4. Conclusion
Bio waste bagasse is converted into carbon (BC) and further
converted into nitrogen doped carbon (NBC) using melamine as
nitrogen source. NBC were prepared with varying weight ratios of
BC: Melamine as 1:5, 1:10, 1:15 and 1:20. When BC: Melamine ratio
is 1:15, nitrogen doped graphene-like carbon sheets (NBC-15) are
obtained. Further, S@NBC cathodes were prepared by absorption of
colloidal sulfur on to NBC carbons. Further, we studied electro-
chemical performance of S@BC, S@NBC-10, S@NBC-15 and S@NBC-
20 composite cathodes by assembling Li-S cells. It has been found
that S@NBC-15 shows the best performance with a reversible ca-
pacity of 1169 mAh g
1 at 0.2 C and maintained to 898 mAh g
1
after 200 cycles with the 77% capacity retention also it shows
remarkable higher order polysulfide retention of 85% over 200
cycles. Additionally, it shows excellent rate capacity of 454 mAh g
1
at 4 C rate. Moreover, to increase the areal sulfur loading, we
adopted the strategy of multiple cathode layer stacking. The two
layer stacked cathode shows very good cycling stability over 500
cycles with sulfur loading amounts to 6 mg cm
2. Using this
approach, sulfur loading is further increased to 12 mg cm
2 by
stacking four cathode layers. The cell shows an areal capacity of 12
mAh cm
2 which is three times higher than the present day lithium
ion batteries.
Notes
The authors declare no competing financial interest.
Acknowledgements
Bosu Babu Dasari thanks Council of Scientific and Industrial
Research (CSIR), India for CSIR-UGC fellowship (23/12/2012(ii) EU-
589
V). The authors thank the Central Instrumentation Facility, CSIR-
CECRI, Karaikudi for providing characterization facilities.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2018.12.101.
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