See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/236048348

Hydrothermal carbon-based nanostructured hollow spheres as electrode

materials for high-power lithium-sulfur batteries

Article  in  Physical Chemistry Chemical Physics · March 2013

DOI: 10.1039/c3cp50653c · Source: PubMed

CITATIONS READS

118 417

6 authors, including:

Nicolas Brun Magda Titirici

French National Centre for Scientific Research Imperial College London
86 PUBLICATIONS   2,112 CITATIONS    218 PUBLICATIONS   15,782 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Sustainable Energy Conversion and Storage View project

precious High Entropy Alloys View project

All content following this page was uploaded by Magda Titirici on 20 May 2014.

The user has requested enhancement of the downloaded file.

 PCCP
View Article Online
PAPER View Journal | View Issue

Hydrothermal carbon-based nanostructured hollow

Cite this: Phys. Chem. Chem. Phys., 2013,
spheres as electrode materials for high-power
15, 6080
lithium–sulfur batteries†
Published on 14 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CP50653C

Nicolas Brun,za Ken Sakaushi,z*bc Linghui Yu,a Lars Giebeler,b Jürgen Eckertbd and
Downloaded by Queen Mary, University of London on 09/04/2013 19:31:06.

Magdalena M. Titirici*e

Received 19th December 2012,
Accepted 13th February 2013
DOI: 10.1039/c3cp50653c
www.rsc.org/pccp
Carbon hollow spheres were produced using a sustainable approach, i.e. hydrothermal carbonization,
using monosaccharides as carbon precursors and silica nanoparticles as hard-templates. Hydrothermal
carbonization is an eco-efficient and cost-effective route to synthesize nanostructured carbonaceous
materials from abundant biomass-derived molecules. After further thermal treatment under an inert
atmosphere and removal of the silica-based core by chemical etching, porous hollow spheres depicting
5–8 nm thin shells were obtained. Subsequently, carbon–sulfur composites were synthesized via a melt
diffusion method and used as nanostructured composites for cathodes in lithium–sulfur (Li–S) cells. The
morphology of the hollow spheres was controlled and optimized to achieve improved electrochemical
properties. Both high specific energies and high specific powers were obtained, due to the unique
nanostructure of the hollow spheres. These results revealed that using optimized carbonaceous
materials, it is possible to design sustainable Li–S cells showing promising electrochemical properties.

Introduction charge–discharge process represent a main drawback for

Due to environmental, economic and societal needs, innovative
and sustainable devices for energy storage and conversion have
constituted a major field of research for the last two decades.1–3
Particularly, lithium-ion batteries have been the center of attention4
as this technology was seen to offer higher energy and power
densities as compared with the traditional Ni–MH and Pb acid
batteries, while leading to a longer life cycle, improved safety and
low self-discharge. However, inherent capacity limitations related
to the Li intercalation–deintercalation reactions involved in the
a
Max-Planck Institute of Colloids and Interfaces, Am Muehlenberg,
D-14476 Potsdam, Germany
b
IFW Dresden, Institute for Complex Materials, Helmholtzstr. 20, D-01069 Dresden,
Germany. E-mail: k.sakaushi@ifw-dresden.de; Fax: +49 351 4659 452
c
TU Dresden, Department of Inorganic Chemistry, Bergstr. 66, D-01069 Dresden,
Germany
d
TU Dresden, Institute of Materials Science, Helmholtzstr. 7, D-01069 Dresden,
Germany
e
Queen Mary University of London, School of Materials Science and Engineering,
Mile End Road, E1 4NS, London, UK. E-mail: m.m.titirici@qmul.ac.uk,
Magdalena.Titirici@mpikg.mpg.de
† Electronic supplementary information (ESI) available: TG measurement, XRD
measurement, comparison of the rate capability, and calculation of the specific
energy and the specific power. See DOI: 10.1039/c3cp50653c
‡ These authors have equally contributed to this study.
the application of lithium-based rechargeable batteries
in large-scale storage and motorized vehicles.5,6 Despite the
development of novel nanostructured electrode materials,7–12 it
remains arduous to reach high energy density while meeting
the requirements as far as safety hazard and cost are concerned.
Moreover, heavy-weight transition-metals are traditionally used
at the cathode side, making an improvement of the specific
capacity difficult.13–15
More recently, the lithium–sulfur (Li–S) technology has been
identified as one of the most promising candidates to overcome
the above issues.16,17 Sulfur is a light-weight element, leading
to Li–S cells exhibiting significantly higher theoretical specific
capacity and energy density than Li-ion batteries, up to
1675 mA h g1 and 2567 W h kg1 respectively.16,17 In addition,
the natural abundance and relative low cost of sulfur make this
technology noticeably attractive as a leading candidate to
design the next-generation of renewable storage devices for
use in electronic vehicles and large-scale storage.6,16,17 How-
ever, the insulating nature of sulfur together with the high
solubility of sulfide-based intermediates generated during the
charge–discharge process involve the development of new
electrolytes,18,19 the design of composites via the addition of
absorbents20 or additives,21–23 and/or the encapsulation of
sulfur within porous conductive hosts.24–26

6080 Phys. Chem. Chem. Phys., 2013, 15, 6080--6087 This journal is c the Owner Societies 2013
 View Article Online

Paper PCCP

In response to these challenges, particularly carbon-based

nanomaterials from cheap renewable sources constitute a rational
solution for the preparation of sustainable carbon–sulfur compo-
site electrodes. In this context, the hydrothermal carbonization
(HTC) of biomass molecules,27–29 mainly monosaccharides such
as glucose or xylose, leading to the production of functional
carbonaceous materials has been established as an interesting
tool for the design of high-performance electrode materials
through an eco-friendly and cheap synthetic pathway.30,31 Porous
carbons have been proposed to improve charge–discharge
cycling properties and specific capacities due to the sorption
of polysulfides and the generation of electronic contact with
sulfur.16,17,32 Particularly, the use of carbon hollow spheres has
Published on 14 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CP50653C

led to high-power Li–S batteries.33a The next challenge is the

Downloaded by Queen Mary, University of London on 09/04/2013 19:31:06.

design of new carbonaceous materials which can achieve both a

high specific energy and a high specific power with improved
cycle performance.
In this study, we describe a sustainable and cost-effective
strategy to improve the electrochemical properties of Li–S
systems: the design of nanostructured hollow spheres (HSs)
templated from Stöber silica nanoparticles through the hydro-
thermal carbonization of abundant biomass-derived molecules
(i.e. monosaccharides). Using this synthetic route, we obtained
nanostructured carbon hollow spheres (HSs) with a diameter of
B80 nm and a good control over the porosity and the shell
thickness. To the best of our knowledge, our carbon HSs exhibit
one of the thinner porous shells (B5 nm), as compared to
other reports.33a,34 For a nice review on micro-/nano-structured
hollow spheres for energy applications please see ref. 33b. Such
nanostructures used as electrode materials are really important
since they can strongly affect the electrochemical reactions
involved. For example, it has been shown that an increase in
surface area, induced by smaller particles size or thinner hollow
shells, can sensibly improve the electrolyte filling. In this direction,
we expect that a fine control over nanoparticle diameter and shell
thickness could lead to optimized morphologies and, as a direct
consequence to improved electrochemical properties. Beyond
the fastidious characterization of these nanostructured materials,
carbon–sulfur composites were synthesized via a melt diffusion
Fig. 1 Micrographs obtained by transmission electron microscopy of (a–b) silica
method and investigated as cathodes for Li–S cells. In this way, a
nanoparticles synthesized via a Stöber process, (c–e) carbon-based hollow spheres
high energy density together with a high rate capability and obtained after hydrothermal treatment at 180 1C in the presence of xylose,
improved cycle properties were obtained. We believe that these pyrolysis at 550 1C and silica removal, 550-CarbHS-X and (f–g) carbon-based
concomitant features are mainly due to the prevention of inter- hollow spheres obtained after hydrothermal treatment at 180 1C in the presence
mediate polysulfides dissolution into the electrolyte, together with of xylose, pyrolysis at 950 1C and silica removal, 950-CarbHS-X. (h–i) Carbon-based
hollow spheres obtained after hydrothermal treatment at 180 1C in the presence
the enhancement of electronic contacts with sulfur.
of glucose, pyrolysis at 950 1C and silica removal, 950-CarbHS-G. Red arrows
highlight the presence of residual silica within the carbon hollow spheres.
Results and discussion
Carbon-based hollow spheres design via hydrothermal silica-based NPs, they were initially amino-functionalized via a
carbonization post-grafting process (see the Experimental section and Table 1
The study presented herein focuses on the design of carbon- (entry 1)). Indeed, by shifting the isoelectric point of the silica-
based hollow spheres (HSs) through the use of 90 nm diameter based particles from pH 2 to pH 5, electrostatic attraction forces
Stöber silica nanoparticles (NPs) as hard-templates (Fig. 1a and b) between positively charged NH2–SiO2 templates and negatively
and hydrothermally carbonized monosaccharides (i.e., glucose charged saccharide-based nuclei were largely favored.35 After
or xylose) as carbon precursors. As previously reported by Ikeda hydrothermal treatment for 20 h at 180 1C and further carboni-
et al.35 to carry out an effective hydrothermal carbon coating of zation at 950 1C under an inert atmosphere, thermogravimetric

This journal is c the Owner Societies 2013 Phys. Chem. Chem. Phys., 2013, 15, 6080--6087 6081
 View Article Online

PCCP Paper

Table 1 Characterization of amino-functionalized silica templates, silica–carbon to generate different products, e.g. 5-(hydroxymethyl)furfural
nanocomposites (950-Carb-X and -G) and carbon-based hollow spheres (550- and furfural respectively.28 Then, in our system the nucleation
CarbHS-X, 950-CarbHS-X and -G) after washing the composites twice overnight
process is expected to be initiated through Maillard reactions
in a solution of ammonium hydrogen difluoride at 4 mol%
between dehydrated sugars and amino-groups anchored on the
Entry Sample Ca Ha Na SiO2b (wt%) inorganic particles. Finally, the polymerization–carbonization
1 NH2–SiO2 90 nm 3.15 1.84 1.74 89.34 process leads to cross-linked furan-based coatings, whose
2 550-CarbHS-X 86.88 3.38 0.49 3.15 chemical structure is closely related to the saccharide used.
3 950-Carb-X — — — 71.69
Indeed, it has been shown that xylose generates more aromatic
4 950-CarbHS-X 93.25 1.56 0.71 3.98
5 550-CarbHS-G 80.7 5.55 3.22 7.15 hydrothermal carbons than glucose, leading to higher carbon
6 950-Carb-G — — — 74.06 content. This feature is supported by TGA carried out on 950-
7 950-CarbHS-G 84.76 1.74 3.77 7.13 Carb-X and 950-Carb-G core–shell nanoparticles, showing that
a b
From elemental analysis. From thermogravimetric measurements. the silica–HTC composites made from xylose exhibit a higher
Published on 14 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CP50653C

HTC content (related to a lower silica content; Table 1 (entries 3

Downloaded by Queen Mary, University of London on 09/04/2013 19:31:06.

and 6)). This could explain thinner and denser coated shells.
measurements showed that the silica@carbon composites were Another major difference related to the monosaccharide in
made up of 83–85 wt% of NH2–SiO2 and 15–17 wt% of carbon use was highlighted by the nitrogen sorption measurements
coating (Table 1 (entries 1, 3 and 6)). (Fig. 2 and Table 2). Beyond similar type IV isotherm profiles
After silica removal by etching, homogeneous carbon-based (Fig. 2), indicative of well-developed meso-macropore systems, a
HSs were obtained (Fig. 1c–i). The as-synthesized HSs have an large gain in both BET surface area and total pore volume was
external diameter of 90–95 nm and an average carbon-shell noticed for the 950-CarbHS-X sample as compared to the spheres
thickness from 5 up to 8 nm, depending on the synthetic synthesized from glucose (Table 2). The dissimilar chemical
pathway. It appears that using xylose as a carbon precursor,
an increase in the further carbonization temperature from 550
to 950 1C leads to a decrease in the shell thickness from 7–8
(Fig. 1e) to 5 nm (Fig. 1g). At the same time, it is interesting to
notice that the internal diameter did not change (i.e., 80 nm),
suggesting that the silica template is thermally stable after
550 1C, since the associated thermal shrinkage is negligible.
Depending on the monosaccharide in use (glucose versus
xylose), a difference can also be observed (Fig. 1f–i). Indeed,
considering the same experimental procedure and after further
carbonization at 950 1C, the hollow spheres made from glucose,
950-CarbHS-G, present a thicker carbon shell (about 7–8 nm,
Fig. 1i) than their analogues made from xylose, 950-CarbHS-X
(Fig. 1g). As a direct consequence, silica removal in a 4 mol%
ammonium hydrogen difluoride aqueous solution appears more
strenuous for 950-CarbHS-G samples than for 950-CarbHS-X, as
shown in Fig. 1h. Indeed, the red arrows highlight the presence
of residual silica within the carbon HS. This feature is also
supported by elemental analysis and thermogravimetric
measurements (Table 1 (entries 4 and 7)), which emphasize a
lower carbon content together with a higher silica loading for Fig. 2 Nitrogen sorption isotherms and DFT pore size distributions of the
the 950-CarbHS-G sample. carbon-based hollow spheres after further thermal treatment at 950 1C
In addition, we can notice that after the first etching process and silica removal obtained from xylose, 950-CarbHS-X (a–b) and from glucose,
overnight, 950-CarbHS-G sample exhibited more than 24 wt% 950-CarbHS-G (c–d).

of residual silica, while 950-CarbHS-X hollow spheres already

reached a silica loading lower than 4 wt%. Thus, we can assume
that the carbon-shell thickness plays an important role in kinetic Table 2 Nitrogen sorption data
diffusion of both ammonium hydrogen difluoride and generated
BET surface Total pore volume
fluorosilicic species within the nanostructured hollow spheres,
Sample area (m2 g1) (cm3 g1)a
particularly due to the hydrophobic nature of the shell. Never-
550-CarbHS-X 534 1.60
theless, an important question may arise. Why is there a
950-CarbHS-X 996 2.88
significant difference in shell thickness and/or permeability 550-CarbHS-G 529 0.58
depending on the monosaccharide used as a carbon precursor? 950-CarbHS-G 296 0.65
To explain this behaviour, it is important to remember that a
Values extracted from the Quenched Solid Density Functional Theory
hydrothermal dehydrations of glucose and xylose are assumed (QSDFT).

6082 Phys. Chem. Chem. Phys., 2013, 15, 6080--6087 This journal is c the Owner Societies 2013

Paper
structures of the hydrothermal carbons mentioned previously
are most probably also involved in this feature.
Indeed, as shown by nitrogen sorption experiments performed
on 550-CarbHS-X and 550-CarbHS-G samples (Table 2 and Fig. S1,
ESI†), the hollow spheres made from glucose exhibit, after further
thermal treatment at 550 1C, a main microporous contribution
centred at 0.8 nm, while the ones made from xylose are essentially
mesoporous (highlighted by a similar BET surface area but a largely
higher total pore volume; Table 2). It has to be noticed that these
samples present sensibly higher BET surface area and total pore
volume than the analogous materials synthesized without silica
hard-templates.41 We assume that the presence of an inorganic
Published on 14 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CP50653C
core during the thermal treatment, minimizing the overall shrink-
Downloaded by Queen Mary, University of London on 09/04/2013 19:31:06.
age of the particles, highly affects the porous structure of the
carbon shells. Thus, the pores generated by physical activation
are slightly wider than the ones obtained for typical hydrothermal
carbons.41 Moreover, the fact that the 550-CarbHS-X hollow spheres
present wider pores than the 550-CarbHS-G particles is in good
agreement with the characterization study recently conducted by
Yu et al.,41 showing that the hydrothermal carbons made from
xylose and post-treated at 550 1C present broader micropores.
From 550 to 950 1C, it has been shown by TEM that the overall
shrinkage of the inner silica particles was negligible. Thus, we
can assume that the protective role of the inorganic core in the
carbon shell porosity is even more important. Indeed, while the
analogous materials synthesized without silica hard-templates
are mainly microporous,41 the 950-CarbHS-X and 950-CarbHS-G
samples are only mesoporous (Fig. 2b and d). The DFT pore size
distributions of these carbon-based hollow spheres depict
consistently a main mesopores contribution centred at 4 nm
(Fig. 2b and d). At the same time, the difference related to
the monosaccharide in use is even more noticeable (Table 2),
probably induced by the synergetic effect of physical activation
during carbonization under an inert atmosphere at 950 1C, and
the silica hard template playing a protective role in shrinkage of
the carbonaceous framework. While the microporous contribu-
tion noticed for the 550-CarbHS-G samples disappeared after the
thermal treatment at 950 1C (Fig. 2d), the mesoporosity is largely
promoted within the carbon shells of the 950-CarbHS-G particles
(Table 2), leading to a large decrease in the surface area. This
feature is directly associated with the initial density, thickness and
chemical structure of the HTC shells. At this stage, it is also
important to notice that the presence of residual silica within the
hollow spheres noticeably affects the porosity measured for each
sample, particularly for the one made from glucose presenting the
higher silica content. As a direct consequence, it is obvious that
higher is the silica content, lower is the overall porosity measured.
Due to an inherent conductivity gained at 950 1C36 and really
interesting nanostructures, these new carbon-based hollow
spheres represent promising candidates as hosts for the encap-
sulation of sulfur for the design of lithium–sulfur battery
cathodes.
Carbon–sulfur composites as cathodes for Li–S batteries
As mentioned before, two main drawbacks have to be overcome
for the design of sustainable Li–S batteries: (i) a low power
This journal is c the Owner Societies 2013
View Article Online
PCCP
density due to the bad electronic transport properties of the
cathode due to the insulating nature of sulfur; and (ii) the
dissolution of intermediate polysulfides into electrolytes and
the following shuttle-effect, involving a capacity fading and a
worse coulombic efficiency.16–20,23,32,33a The strategy developed
in our work is to use the porous carbon HS presented before-
hand to design carbon–sulfur composites via a melt diffusion
method, in such a way that: (i) the nanostructured conductive
shells enhance the electronic transport properties due to a
better electronic contact with sulfur,32,33a,37 increasing both
the specific capacity and the rate capability; (ii) the HS having a
porous-network prevents the dissolution of intermediate poly-
sulfides into electrolytes, improving the charge–discharge cycle
property and the coulombic efficiency. These two main features
are expected to work co-operatively and lead to Li–S cells with
high-performance electrochemical properties.
First of all, we have compared two series of nanospheres
exhibiting different shell nanostructures, depending on the
monosaccharide used. All electrochemical properties were
measured using cathodes with a fixed carbon : sulfur weight
ratio of 1 : 1 (see Fig. S2, ESI†) and the specific capacities were
calculated based on the mass of sulfur. Fig. 3a and b show the
1st and 5th charge–discharge curves at a low current density of
0.1 C (= 167.5 mA g1) for the electrodes using 950-CarbHS-X
and 950-CarbHS-G, respectively. Both carbon nanospheres
showed a specific capacity of B1300 mA h g1 at the 1st
discharge, which suggests an electrically well conductive
carbon–sulfur network in the cathode. The first plateau at
around 2.4 V vs. Li/Li+ is attributed to the conversion of solid
sulfur to soluble polysulfides. The next plateau at around 2.1 V
vs. Li/Li+ suggests the conversion of polysulfides to solid
LixS.16,17 The main difference occurred after the 1st cycle. The
950-CarbHS-X showed a shuttle-effect which suggests the
dissolution of polysulfide species into the electrolyte. In contrast,
the 950-CarbHS-G showed a coulombic efficiency (CE) of almost
100% until the 20th cycle. To explain this significant difference
in electrochemical behavior, various parameters can be
considered. Firstly, previous research has suggested that even
a small amount of SiOx (i.e. 2 wt%) can improve the cycle ability
by avoiding the shuttle-effect.37 In our case, both HSs contain
residual SiO2 (Table 1), especially the 950-CarbHS-G nano-
spheres, which depict a silica loading almost twice higher than
950-CarbHS-X. Therefore, we can conclude that residual SiO2
is probably partially responsible for the difference in electro-
chemical properties between 950-CarbHS-X and 950-CarbHS-G
samples. Secondly, we focused on the porous characteristics of
the carbon shells (Fig. 2 and Table 2).
Although it has been suggested that both high surface areas
and large pore volumes enhance the loading of sulfur into
porous materials,17,32,37,38 it remains delicate to consider an
eventual influence on cycle performances.26,39,40 Nevertheless,
we can assume that, while enhancing the carbon–sulfur inter-
face, an increase in the specific surface area of the conductive
host concomitantly involves a significant rise in the sulfur–
electrolyte interface, favoring henceforth the dissolution of
intermediate polysulfides and the following shuttle-effect.
Phys. Chem. Chem. Phys., 2013, 15, 6080--6087 6083

PCCP
Published on 14 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CP50653C
Downloaded by Queen Mary, University of London on 09/04/2013 19:31:06.
Fig. 3 Electrochemical characterization of the two different carbon nano-
spheres. (a) Charge–discharge curves for electrodes using 950-CarbHS-X at a
current density of 0.1 C (= 167.5 mA g1). (b) Charge–discharge curves for
electrodes using 950-CarbHS-G at a current density of 0.1 C (= 167.5 mA g1).
(c) Coulombic efficiency for electrodes using 950-CarbHS-X (indicated by
filled squares) and 950-CarbHS-G (indicated by hollow diamonds), respectively.
Each specific capacity in (a) and (b) was calculated based on the mass of sulfur.
Lastly, carbon hollow spheres with shells thicker than 50 nm
have shown very stable charge–discharge properties.37 From
those reports and our results, we can conclude that the
950-CarbHS-G displays better charge–discharge properties
compared to 950-CarbHS-X also due to a thicker shell.
As 950-CarbHS-G nanospheres present the most promising
results to prevent dissolution of polysulfides within the electro-
lyte, we focused most precisely on this material in the following
study. Fig. 4 shows cycling properties at 1 C (= 1675 mA g1) up
to the 50th cycle of the 950-CarbHS-G/S composite made by a
melt diffusion method, the mixture of 950-CarbHS-G and S, and
the mixture of HTC microspheres made from glucose without
templates and S.
6084 Phys. Chem. Chem. Phys., 2013, 15, 6080--6087
View Article Online
Paper
Fig. 4 Cycling performances at 1 C for various electrodes using hydrothermal
carbons. The cycling stability of the 950-CarbHS-G–S composite made by melt
diffusion method is indicated by circles. The cycling performance of the mixture of
950-CarbHS-G and S is indicated by squares, while the one associated with the
mixture of HTC non-hollow microspheres and S is indicated by triangles.
These HTC non-hollow microspheres have been previously
described by Yu et al.,41 and were used here as Li–S cathodes
after further thermal treatment at 950 1C under an inert atmo-
sphere, following the same pathway as described for HSs (see
the Experimental section). Contrary to the composite, the
mixtures were made by mechanically mixing powdered sulfur
and carbon compounds without further treatments. By using
these three different carbon–sulfur materials, improvements in
electrochemical properties related to the nanostructure of the
carbon spheres were investigated. As shown in Fig. 4, we can
obtain stable cycling properties by using nanostructured HSs.
This result clearly reveals that the highly porous shells of HSs
work as an absorbent for soluble polysulfides. The higher
specific capacity obtained via a melt diffusion method reveals
the formation of a better conductive contact in the HS–S
composite17,32,33a,37 compared to the mixture of HSs and S.
The results obtained for non-hollow microspheres underlined
two benefits related to the use of HSs in Li–S cells: (i) the
nanosized spheres improve the specific capacity by ensuring
formation of a conductive network in the cathode made by a
composite consisting of carbon spheres, sulfur and binders. If
we compare the specific capacity at the 1st cycle of the mixtures
made of HSs and non-hollow microspheres, the hollow spheres
show a capacity of more than 800 mA h g1 while it remains at
only 300 mA h g1 for non-hollow HTC microspheres; (ii) while
the capacity decreases rapidly for the non-hollow microspheres,
the HS–S composite, which displays a discharge capacity of
1000 mA h g1 at the 1st cycle, maintains a discharge capacity
of 600 mA h g1 at the 50th cycle. The drop in specific capacity
during the first few cycles can be explained by the formation
of S layers on the surface of HSs due to the strong affinity of
sulfur for carbon.37,42 This result reveals that the unique
nanostructure of the hollow nanospheres is the essence of
the high-performance electrochemical properties.
Finally, we investigated the rate capability of the HS–S
composite cathode and observed a remarkably high specific
power of our Li–S systems. The HS–S composite cathode
showed an initial discharge capacity of 1000 mA h g1,
700 mA h g1, and 400 mA h g1 at 1 C (= 1675 mA g1),
This journal is c the Owner Societies 2013

Paper
Published on 14 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CP50653C
Downloaded by Queen Mary, University of London on 09/04/2013 19:31:06.
Fig. 5 (a) Rate performance for 950-CarbHS-G–sulfur electrodes. The specific
capacity was calculated based on the mass of sulfur. (b) Ragone plot for Li–S cells
using the 950-CarbHS-G–sulfur composite electrode. We estimated that a full Li–S
cell using 950-CarbHS-G contains 25 wt% of Li2S for the total device weight.
Details are available in the experimental procedures and Fig. S2 (ESI†). The
theoretical maximum of the specific energy for our full cells was calculated as
follows: 2567 W h kg1  0.25 = 641 W h kg1. The properties of Li–ion batteries
were taken from ref. 44. The references for the specific energy and the specific
power of advanced Li–S cells were taken from ref. 17 and 45.
2.5 C (= 4187.5 mA g1), and 5 C (= 8375 mA g1), respectively.
Even at a very high current density of 10 C (= 16 750 mA g1),
our cathode showed a discharge capacity of 170 mA h g1. The
high rate capability of the HS–S composite cathode is excellent
when compared to other reports (Fig. S3, ESI†). If we assume
that a full Li–S cell using HSs contains 25 wt% of Li2S, this full
cell will provide a specific energy of 460 W h kg1 and a specific
power of 5000 W kg1 (Fig. 5b and Fig. S4, ESI†).
These exceptional results are based on the unique features of
HSs: (i) the highly porous nanostructured shells provide a stable
cycle performance and a high rate capability by adsorbing
polysulfides and improving the Li+ transportation, allowing the
diffusion/filling of the electrolyte within the carbon-based frame-
work; and (ii) the partially graphitized nanosized HSs43 ensure a
good conductive network within the cathode. These results
suggest that the HS–S composite cathode could be a promising
electrode for Li–S systems, providing a specific energy for the full
cell more than 2 times higher than the one typically described
for Li–ion batteries in full cells44 (i.e., about 200 W h kgcell1),
and also, approaching the expected maximum specific energy for
full Li–S battery cells of 700 W h kgcell1.17 Last but not least, we
successfully reached a high specific power by using HSs, which is
a major challenge for Li–S systems.
This journal is c the Owner Societies 2013
View Article Online
PCCP
Conclusions
We have reported here the synthesis of hollow carbon spheres
with thin porous walls using an eco-efficient hydrothermal
carbonization procedure in the presence of amino modified
nanosized silica spheres. Two different biomass-derived molecules
were employed as a carbon source during the hydrothermal
carbonization process, i.e. glucose and xylose. The resulting carbon
hollow spheres from glucose exhibited thicker carbon walls as
compared to the ones from xylose. Following further heat treatment
at 950 1C to improve the conductivity and infiltration with sulfur
via a melt diffusion method, the two hollow carbon spheres–
sulfur composites were tested as a cathode in Li–S batteries. The
xylose-derived material showed a shuttle-effect, which suggests
the dissolution of polysulfide species into the electrolyte.
In contrast, the glucose hollow spheres showed a coulombic
efficiency (CE) of almost 100% until the 20th cycle. We attributed
that to a higher amount of residual silica present in this
material, known to improve the cycle performance in good
agreement with previous literature data. On the other hand the
smaller surface area and the thicker carbon shells in the case of
glucose derived material might play also an important role.
We have also compared the performance of the hollow
spheres with micrometer-sized full spheres obtained under
the exact same conditions from the hydrothermal carbonization
of glucose without the use of silica templates. From this compar-
ison we could show: (i) the highly porous shells of HSs work as an
absorbent for soluble polysulfides; (ii) the infiltration of sulfur
using the melt diffusion method reveals the formation of a better
conductive contact in the HS–S composite compared to the simple
mixture of HSs and S.
Experimental section
Materials
D-(+)-Glucose 99% and D-(+)-xylose 99% anhydrous were purchased,
respectively, from Roth Chemicals and Sigma Aldrich. Tetraethyl
orthosilicate (TEOS), (3-aminopropyl) triethoxysilane (APTES) and
ammonium hydrogen difluoride (NH4HF2) were purchased from
Sigma Aldrich. Ammonium hydroxide (NH4OH) extra pure 25% in
water was purchased from Acros Organic.
Synthesis and functionalization of silica nanoparticles (Stöber
process)
Synthesis. In a typical synthesis, to a mixture composed of
169 mL of absolute ethanol, 14.4 mL of water and 7.8 mL of NH4OH
(25%), 8.86 mL of TEOS are added drop-by-drop (1–2 minutes)
under vigorous magnetic stirring, to reach the final concentrations
(in ethanol): 0.2 M TEOS, 0.5 M NH3, and 5 M H2O. After
30 minutes, the magnetic stirring is decreased to reduce poly-
dispersity of the silica particles, and the solution is left for
12–20 hours to complete condensation. The nanoparticles (NPs)
are then successively centrifuged and washed a few times in absolute
ethanol, to remove the residual water, NH4OH and TEOS.
Functionalization. Typically, to 200 mL of a SiO2 alcoholic
solution, corresponding to a mass of nanoparticles of 2.7 g, was
Phys. Chem. Chem. Phys., 2013, 15, 6080--6087 6085

PCCP
added 2.8 mL of APTES. The solution was left for 24 hours under
magnetic stirring at room temperature, then successively centrifuged
and washed a few times in absolute ethanol to remove residual
APTES. Finally, the amino-SiO2 nanoparticles were dispersed in
water via successive centrifugation and washing steps.
Synthesis of carbon-based hollow spheres
Typically, 0.3 g of xylose or glucose was added to 10 mL of an
aqueous solution of amino-NPs (corresponding to a mass of
NPs of 120 mg). After vigorous stirring for a few minutes, the
solutions were then added in a glass inlet (30 mL volume)
sealed in a Teflon lined autoclave (45 mL volume) and placed in
Published on 14 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CP50653C
a laboratory oven preheated to the desired temperature (e.g.
Downloaded by Queen Mary, University of London on 09/04/2013 19:31:06.
180 1C) and left for the desired reaction time (e.g. 20 h). The
powders obtained were then removed from the glass inlets, and
successively centrifuged and washed a few times in water and
absolute ethanol, to remove the residual unreacted precursors
and by-products. The carbon-coated silica-based nanoparticles
were then placed in a ceramic crucible in a carbonization oven
and heated to the desired temperature (e.g. 550 or 950 1C)
under an inert atmosphere (i.e. N2 flow: 10 mL min1).
Concerning the thermal treatment at 950 1C, the following
program was used: a first ramp to reach 350 1C at a speed of
5 1C per minute, a second ramp to reach 950 1C at 2 1C per
minute and an isothermal step of 2 h. Concerning the thermal
treatment at 550 1C, the desired temperature was reached at a
speed of 2 1C per minute and an isothermal step of 4 h was
used. Samples were then allowed to cool to ambient conditions,
removed from the oven and washed twice overnight in a
solution of ammonium hydrogen difluoride at 4 mol% (i.e.
2.2 mol L1) to remove the silica template. The as-synthesized
carbon-based hollow spheres were named 550- or 950-CarbHS-
P, with P corresponding to the carbon precursor used, with
P = X or G, respectively, for xylose or glucose.
Characterization
Elemental analysis (EA) data were obtained from a Vario El
elemental analyzer. Electrical conductivity measurements were
carried out with a Gamry Reference 600/3000 potentiostat
(Gamry Instruments), applying an R-model for potentiostatic
impedance spectroscopy at 1–1000 Hz using a two electrode
set-up. N2 sorption analysis was performed at 77 K using a
QUADROSORB SI, equipped with an automated surface area
and pore size analyzer. Before analysis, samples were degassed
at 150 1C for 20 h using a ‘‘Masterprep’’ degassing system. BET
surface areas were determined over a P/P0 range as described
previously. Pore size distributions (PSD) were calculated using
Quenched Solid Density Functional Theory (QSDFT), as this
evaluation model takes into account the effects of surface
roughness and chemical heterogeneity of surfaces. Transmis-
sion Electron Microscopy (TEM) was carried out with a Carl
Zeiss Omega 912X at an acceleration voltage of 120 kV.
Electrochemistry
Carbon-based hollow nanospheres–sulfur composites (with a
fixed carbon : sulfur weight ratio of 1 : 1) were prepared by a
6086 Phys. Chem. Chem. Phys., 2013, 15, 6080--6087
View Article Online
Paper
melt diffusion method.32 Carbon and sulfur were ground
together and heated to 155 1C in an Ar atmosphere. The
electrodes were made by the C–S composite (90 wt%) and
binder (polyvinylidene difluoride; 10 wt%). We assembled the
two-electrode Swagelok-type cells in an argon-filled glove
box and tested them on a multichannel potentiostatic–galvano-
static system (VMP-3, Bio-Logic) at 25 1C. Lithium metal
was used as an anode and 1 M LiN(SO2CF3)2 (LiTFSI) in
1,3-dioxolane and 1,2-dimethoxyethane (volume ratio 1 : 1) as
an electrolyte. We calculated specific energy E (W h kg1) and
specific power P (W kg1) by the following method: E (W h kg1)
R t I0
can be calculated from E ¼ 0cut VðtÞdt, where tcut (hour) is
m
the discharge time, I0 (A) is the constant current, m (kg) is the
mass of active materials, and V(t) is the time-dependent voltage
in the dimension of V. Specific power P (W kg1) can be
calculated by P = E/tcut. To describe the Ragone plot, we used
the mass of Li2S and assumed that the mass of Li2S will
comprise 25 wt% of the total device weight.
Acknowledgements
K.S. thanks Martin Zier (IFW Dresden, ICM) and Georg Nickerl
(TU Dresden) for their support. K.S. is financially supported by
DAAD (A/09/74990). N.B. would like to thank Irina Shekova
and Silvia Pirok (Max-Planck Institute of Colloids, Golm) for
thermogravimetric measurements and elemental analysis, and
Pr. Luis Liz-Marzán (Centre for Cooperative Research in Bio-
materials-CIC biomaGUNE, San Sebastián, Spain) for helpful
discussions concerning silica nanoparticles synthesis. We are
grateful to the Max Planck Society for financial support.
Notes and references
1 A. S. Arico, P. Bruce, B. Scrosati, J.-M. Tarascon and W. Van
Schalkwijk, Nat. Mater., 2005, 4, 366.
2 M. S. Whittingham, Mater. Res. Bull., 2008, 33, 411.
3 B. Dunn, H. Kamath and J.-M. Tarascon, Science, 2011,
334, 928.
4 J.-M. Tarascon and M. Armand, Nature, 2001, 414, 359.
5 M. Armand and J.-M. Tarascon, Nature, 2008, 451, 652.
6 J.-M. Tarascon, Philos. Trans. R. Soc., A, 2010, 368, 3227.
7 P. Poizot, S. Laruelle, S. Grugeon, L. Dupont and
J.-M. Tarascon, Nature, 2000, 407, 496.
8 P. G. Bruce, B. Scrosati and J.-M. Tarascon, Angew. Chem.,
Int. Ed., 2008, 47, 2930.
9 E. Hosono, T. Kudo, I. Honma, H. Matsuda and H. S. Zhou,
Nano Lett., 2009, 9, 1045.
10 B. Kang and G. Ceder, Nature, 2009, 458, 190.
11 M. Okubo, Y. Mizuno, H. Yamada, J. Kim, E. Hosono,
H. Zhou, T. Kudo and I. Honma, ACS Nano, 2010, 4, 741.
12 L. Ji, Z. Lin, M. Alcoutlabi and X. Zhang, Energy Environ. Sci.,
2011, 4, 2682.
13 M. S. Whittingham, Chem. Rev., 2004, 104, 4271.
14 Y. Wang, P. He and H. Zhou, Energy Environ. Sci., 2011,
4, 805.
This journal is c the Owner Societies 2013

Paper
15 K. Sakaushi, G. Nickerl, F. M. Wisser, D. Nishio-Hamane,
H. S. Zhou, S. Kaskel and J. Eckert, Angew. Chem., Int. Ed.,
2012, 51, 7850.
16 P. G. Bruce, S. A. Freunberger, L. J. Hardwick and
J.-M. Tarascon, Nat. Mater., 2012, 11, 19.
17 X. Ji and L. F. Nazar, J. Mater. Chem., 2010, 20, 9821.
18 J. H. Shin and E. J. Cairns, J. Power Sources, 2008, 177, 537.
19 M. Hagen, S. Dofler, H. Althues, J. Tubke, M. J. Hoffmann,
S. Kaskel and K. Pinkwart, J. Power Sources, 2012, 213, 239.
20 X. Ji, S. Evers, R. Black and L. F. Nazar, Nat. Commun., 2011,
2, 325.
21 M. S. Song, S. C. Han, H. S. Kim, J. H. Kim, K. T. Kim,
Y. M. Kang, H. J. Ahn, S. X. Dou and J. Y. Lee, J. Electrochem.
Published on 14 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CP50653C
Downloaded by Queen Mary, University of London on 09/04/2013 19:31:06.
Soc., 2004, 151, A791.
22 W. Zheng, Y. W. Liu, X. G. Hu and C. F. Zhang, Electrochim.
Acta, 2006, 51, 1330.
23 D. Aurbach, E. Pollak, R. Elazari, G. Salitra, C. S. Kelley and
J. Affinito, J. Electrochem. Soc., 2009, 8, A694.
24 J. Wang, J. Yang, C. Wan, K. Du, J. Xie and N. Xu, Adv. Funct.
Mater., 2003, 13, 487.
25 B. Zhang, X. Qin, G. R. Li and X. P. Gao, Energy Environ. Sci.,
2010, 3, 1531.
26 S. Dorfler, M. Hagen, H. Althues, J. Tubke, S. Kaskel and
M. J. Hoffmann, Chem. Commun., 2012, 48, 4097.
27 M.-M. Titirici, A. Thomas and M. Antonietti, New J. Chem.,
2007, 31, 787.
28 M.-M. Titirici, M. Antonietti and N. Baccile, Green Chem.,
2008, 10, 1204.
29 M. Sevilla and A. B. Fuertes, Chem.–Eur. J., 2009, 15, 4195.
30 Y.-S. Hu, R. Demir-Cakan, M.-M. Titirici, J.-O. Muller,
R. Schlogl, M. Antonietti and J. Maier, Angew. Chem., Int.
Ed., 2008, 47, 1645.
This journal is c the Owner Societies 2013
View publication stats
View Article Online
PCCP
31 K. Tang, R. J. White, X. Mu, M.-M. Titirici, P. A. Van Aken
and J. Maier, ChemSusChem, 2012, 5, 400.
32 X. Ji, K. T. Lee and L. F. Nazar, Nat. Mater., 2009, 8, 500.
33 (a) N. Jayaprakash, J. Shen, S. S. Moganty, A. Corona and
L. A. Archer, Angew. Chem., Int. Ed., 2011, 50, 5904; (b) X. Lai,
J. E. Halpert and D. Wang, Energy Environ. Sci., 2012,
5, 5604.
34 R. J. White, K. Tauer, M. Antonietti and M.-M. Titirici, J. Am.
Chem. Soc., 2010, 132, 17360.
35 S. Ikeda, K. Tachi, Y. H. Ng, Y. Ikoma, T. Sakata, H. Mori,
T. Harada and M. Matsumura, Chem. Mater., 2007, 19, 4335.
36 S.-A. Wohlgemuth, R. J. White, M.-G. Willinger, M.-M. Titirici
and M. Antonietti, Green Chem., 2012, 14, 1515.
37 J. Schuster, G. He, B. Mandlmeier, T. Yim, K. T. Lee, T. Bein
and L. F. Nazar, Angew. Chem., Int. Ed., 2012, 51, 3591.
38 C. Liang, N. J. Dudney and J. Y. Howe, Chem. Mater., 2009,
21, 4724.
39 X. Li, Y. Cao, W. Qi, L. V. Saraf, J. Xiao, Z. Nie, J. Mietek,
J. G. Zhang, B. Schwenzer and J. Liu, J. Mater. Chem., 2011,
21, 16603.
40 R. Demir-Cakan, M. Morcrette, F. Nouar, C. Davoisne,
T. Devic, D. Gonbeau, R. Dominko, C. Serre, G. Ferey and
J.-M. Tarascon, J. Am. Chem. Soc., 2011, 133, 16154.
41 L. Yu, C. Falco, J. Weber, R. J. White, J. Y. Howe and
M.-M. Titirici, Langmuir, 2012, 28, 12373.
42 Y. Yang, M. T. McDowell, A. Jackson, J. J. Cha, S. S. Hong
and Y. Cui, Nano Lett., 2010, 10, 1486.
43 K. Tang, L. Fu, R. J. White, L. Yu, M.-M. Titirici,
M. Antonietti and J. Maier, Adv. Energy Mater., 2012, 2, 873.
44 V. Etacheri, R. Marom, R. Elazari, G. Salitra and D. Aurbach,
Energy Environ. Sci., 2011, 4, 3242.
45 http://sionpower.com/pdf/articles/SionPowerECS.pdf.
Phys. Chem. Chem. Phys., 2013, 15, 6080--6087 6087