Colloids and Surfaces A: Physicochem. Eng.

Aspects 414 (2012) 98103

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage:www.elsevier.com/locate/colsurfa

Fabrication of conductive polymer-coated sulfur composite cathode materials

based on layer-by-layer assembly for rechargeable lithiumsulfur batteries
Li Duan

, Jiachun Lu, Wenyuan Liu, Ping Huang, Wushang Wang, Zhichao Liu

Northwest Institute of Nuclear Technology, Xian, Shaanxi 710024, China

highlights

graphical abstract

A novel conductive polymer-coated

sulfur cathode in Li/S battery was
fabricated.
LbL assembly technique was introduced
to encapsulate sulfur
cathode in Li/S battery.
Polymers were coated on the surface of
sulfur only by physical interaction.
The as-prepared sulfur represents a
1

well conductivity of 0.23 S cm .

The sulfur shells with a low permeability were obtained.
cathode materials for rechargeable lithiumsulfur
batteries. Conductive polyaniline (PANI) were
assembled on the outer shell of sulfur particles to
provide an electron conducting paths for the charge
and discharge of lithiumsulfur battery. The low
permeability of sulfur shells was obtained by
assembling the enough number of polyelectrolyte
bilayers. A crosslinker and heat treatment were
utilized to further reduce its permeability. The
assembled polymer shells can be expected to be

abstra
ct
article info
Article history:
Received 22 May 2012
Received in revised form 23 July 2012 Accepted 5 August 2012
Available online 28 August 2012
Keywords:
Lithium/sulfur batteries
Sulfur cathode
Layer-by-layer assembly
Conductive polymer

they
can
powe
1. Introduction
r an
The
development
of
rechargeable incre
batteries with a high energy density and long asing
cycle life is currently of great importance, as ly

Lithium
sulfur battery
is
a
promising
energy
storage
system due
to its high
specific
energy
density, low
cost
and
environmenta
l friendliness.
Layer-bylayer
(LbL)
assembly
technique is
introduced as
a
simple
method
to
fabricate
polymercoated sulfur

diverse
range
applications, from

Correspon

permeable for Li and slowly or hardly for sulfur

and polysulfide during charge and discharge
process. The obtained sulfur composite cathode
materials were characterized by four-point probe
instru-ment, scanning electron microscopy (SEM),
transmission electron microscopy (TEM), X-ray
diffraction (XRD) patterns and Fourier transform
infrared (FTIR) spectroscopy. The results
demonstrated polymers have been coated on the
surface of sulfur only by physical interaction and
have no effect on sulfur. The conductive polymercoated sulfur cathode also represents a well
1

conductivity of 0.23 S cm . Moreover, after coated

by polymers, the crystal structure of sulfur still
keeps
its
orthorhombic
corresponding
to
cyclooctasulfur molecule (S8 ).
2012 Elsevier B.V. All rights reserved.

of

ding author.

E-mail

Tel.: +86 29

address:

84767710;

duanli@icc

fax: +86 29

as.ac.cn (L.

83366333.

Duan).

0927-7757/$ see front matter 2012

Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2012.08.
033

micro
chips
for
small
-size
electr
onic
devic
es, to

power
sources
forenergy 2600 Wh
electrical
vehicles.kg1
on
the
Lithiumsulfur
batteryassumption of the
consisting of sulfur as thecomplete reaction of
cathodes and lithium aslithium with sulfur to
the anodes [1,2] is very
attractive because of itsLi2 S [3]. Besides,
high theoretical specificele-mental sulfur as
1a cathode material
capacity of 1675 mAh g
shows
many
and the-oretical specificadvantages
as

cathode
materials
due
to
its
abundance, low cost
and environmen-tal
friendliness
[4,5].
However,
lithium
sulfur
battery
is
difficult
to
commercialize due to
low sulfur utilization
and poor cycle life

L. Duan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103

electrochemical
performance
in
property. These problems are attributed to the insulating lithiumsulfur batteries. The positively
poly(allylamine
nature of sulfur [6] and the dissolution of lithium polysulfidescharged
2
(Sn , n 4) formed during discharged process into the hydrochloride) (PAH) and negatively
poly(styrenesulfonate
liquid electrolytes [5,710]. The insulating nature of sulfurcharged
sodium
salt)
(PSS) were first
prevents full discharge of a Li/S battery with a 100% sulfur
positive electrode at room tem-perature. The dissolution of alternately adsorbed on the surface
polysulfides can cause self-discharge and poor electronic of sulfur for 10 bilayers. Then, the
conductivity of Li/S battery, resulting in a rapid capacityaniline monomers were polymerized
to a conductive polyaniline on the
fading of lithium battery during cycling.
As one alternatively resolved method, the cathode outer shell of polymer-coated sulfur
materi-als can be well combined with electrical and ionic by the oxidation of ammonium
conducting agent, such as the electro-polymerizedpersulphate
(APS).
The
wall
conductive polyaniline (PANI) and polypyrrole (PPY), which thickness of sulfur composite materiwould improve the batterys rechargeability [1117].als can be well controlled by
Besides, the use of absorbing agent, such as aluminum adjusting the number of assembled
oxide, silicates, vanadium oxides and transition chalco-layers. In order to improve the
genides [18], can effectively prevent the polysulfidespermeability of sulfur shells, the
dissolution due to their large surface. However, these
adsorbing materials are not desirable as additive for
lithium/sulfur cells due to their insu-lating property. The
addition of linear carbon materials, such as multi-walled
carbon nanotubes (MWNTs) and carbon nanofibers, into
sulfur cathode as absorbing agent can also improve cycle
life of lithiumsulfur battery, as they present an effective
electron con-ductivity and a stable network-like structure of
sulfur cathode. However, they are difficult to commercialize
due to their high cost and the complexity of the
manufacturing process. PANI and PPY with special
morphology can well be used as conductive addi-tives,
distribution agents and absorbing agents to enhance the
electrochemical performance of sulfur. So, we targeted our
work on fabricating sulfur composite cathode materials
coated with elec-tronically conductive polymer matrix.
In our previous work, layer-by-layer (LbL) assembly
technique has been successfully applied in the fabrication
of various function-alized microcapsules based on the
different interaction forces, such as electrostatic interaction
[1923] and covalent bond [2430]. The assembled
capsules have well-controlled size, shape, and wall
thickness. A wide range of components such as natural or
syn-thetic macromolecules, nanoparticles and proteins [31]
can be chosen as coating materials. The wall composition
can be readily changed to adjust their physicochemical
property and perme-ability. The typical composition are
mainly positively charged poly(allylamine hydrochloride)
(PAH) and negatively charged poly(styrenesulfonate
sodium salt) (PSS) [19,20]. Moreover, the PAH/PSS
capsules shell has been found to be able to swell and
shrink in response to temperature [20]. Leporatti et al.

demonstrated that during the heating at 70 C for 2 h, the

PAH/PSS capsules shrink remarkably and the wall
becomes thicker. Our previous work also showed that four
bilayers of hollow PDADMAC/PSS capsules at high

temperature (55 and 71 C) are impermeable for 6-CF (Mw

373.62 Da); but at low temperature they are permeable
[22].
The cross-linking agent, such as glutaraldehyde (GA),
can be used to immobilize various macromolecules. The
cross-linked macromolecules can show a higher stability
over a broad range of pH and temperature conditions, and
a more compact structure [24,32]. Thus, this immobilization
method is attractive in its sim-plicity and robustness, as it
offers a good route for enhancing the dense of particle
shells.
Herein, we explored a facile and controllable avenue to
fabricate novel sulfur composite materials with improved

99

glutaraldehyde (GA) was further

utilized to immobilize the shells by the
covalent bond between the aldehyde
groups of GA with the free amino
sites of PAH. The heat treatment was
performed to obtain a thicker and
more contractive sulfur shell.
2. Experimental
2.1. Materials
Polyethyleneimine (PEI, Mw 50
100
kDa),
poly(allylamine
hydrochloride) (PAH) (Mw 70 kDa),
poly(styrenesulfonate sodium salt)
(PSS) (Mw 70 kDa), gultaraldehyde
(GA)
and
the
water-soluble
polypyrrole (PPY) (5 wt% in water)
doped with organic acid were
purchased from SigmaAldrich. The
aniline monomer was used with
further purification by decompressed

distillation and then stored at 05 C.

The water used in all experiments
was prepared in a three-stage
Millipore Milli-Q Plus 185 purification
system and had a resistivity higher
than 18.2 M cm.
2.2. Assembly of
polyelectrolyte multilayers on
the surface of sulfur particles
Sulfur particles were separately
dispersed in PEI solution (1 mg/mL in
0.5 M NaCl) and allowed to adsorb for
30 min. Then excess polyelectrolytes
were removed by centrifugation and
three times washing with 0.5 M NaCl.
Subsequently the above suspensions were alternately dispersed in
PAH and PSS solution (2 mg/mL in
0.5 M NaCl) for another 30 min,
followed by three times washing in
0.5 M NaCl. After the assembly of a
desired number of PAH/PSS layer,
the coated particles were then
dispersed in 5% glutaraldehyde (GA)
aqueous solution for 30 min. Finally
these sample suspensions were
incubated at the high temperature for
20 min.
2.3. Preparation of conductive PANI
and PPY shells
In a typical procedure, the
prepared polymer-coated sulfur particles aqueous dispersion was added
into the aniline monomer solution
mixed with 1 M hydrochloric acid
(HCl) under stirring. After 30 min, the
equivalent number of moles of 22.8
wt%
aque-ous
ammonium
persulphate (APS) solution (with

respect to aniline) was slowly added, followed by an the positively charged outer shell of

oxidative polymerization at 03
C. The reaction was(PAH/PSS)n/PAH-coated
sulfur
carried out for 24 h. The resultant green solid,particles. The resultant gray solid was
PANI/polymer-coated sulfur particles, were obtained bydried for further characterization and
cen-trifugation and washed with water and ethanol testing.
thoroughly to remove excess ions and monomers. The
procedure was repeated to increase the PANI content. The
final product was dried under vacuum at ambient
2.4. Four-point probe instrument
temperature for 24 h. The whole experiments were
performed under the nitrogen atmosphere. The conductive
Conductivity measurements of the
polypyrrole (PPY) shells were prepared through a
electrostatic interaction of the negatively charged PPY oncompressed piece of dry powder
were performed using a standard

four-point probe tech-nique, SZ82

(Baishen Technologies, China), at
room temperature [33].

2.5. SEM
Scanning electron microscopy
(SEM) was applied to observe the
surface
morphology
of
sulfur
particles. Samples were sputtered

100

L. Duan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103

[22,34,35] can decrease the

permeability of capsule
walls, resulting from the
rearrangement
of
the
polymer chains induced by
heating and crosslinking into
a more preferred structure.
This rearrangement process
is accompanied by wall
thickening, condensation of
polyelectrolyte and thus a
distinct decrease of pore
size. So polymer-coated
sulfur particles were subScheme 1. Schematic illustration of the fabrication of
sequently crosslinked by
conductive polymer-coated sulfur as cathode for lithium
glutaraldehyde (GA) and
sulfur batteries by layer-by-layer assembly.

were heated to around 70

with gold and measured using a Quanta 600C. It can be expected that
FEG instrument (FEI, American) at anthe obtained polymer shells
of sulfur are permeable for
operation voltage of 3.0 keV.
very small molecular weight
of lithium ions between the
2.6. TEM
interior and exterior, but
For transmission electron microscopyslowly or hardly per-meable
(TEM) observation, the sulfur particles after for sulfur and polysulfide.
1
also
coated
by
(PAH/PSS)10
PANI
wereScheme
schematically
illustrates
the
redispersed in ethanol by ultrasonic treatment
and dropped on carboncopper grids. TEM recharged process of sulfur
images were collected by using a JEOL JEM as a cathode. During
discharge
and
charge
1011 F micro-scope working at 100 kV.
processes of Li/S batteries,
the redox cou-ple reaction
2.7. XRD
of lithium with sulfur to Li2 S,
X-ray diffraction (XRD) patterns were
16Li + S8 8Li2 S, can
collected on a D/MAX-2400 powder X-ray
diffractmeter operating at 40 kV and 30 mA
and using Cu-K radiation ( = 0.15406 nm).
2.8. FTIR
Fourier
transform
infrared
(FTIR)
spectrum was measured on a Magna 750
spectrometer (Nicolet, American) using KBr
pressed disks.

3. Results and discussion

To search for higher capacity and better
rate performance of lithiumsulfur battery, the
fabrication of appropriate composite cathode
materials is imperative. Here, we controllably
synthe-sized the conductive polymer-coated
sulfur composite materials based on layer-bylayer assembly technique, as shown in
Scheme
1.
The
positively
charged
poly(allylamine hydrochloride) (PAH) and
negatively charged poly(styrenesulfonate
sodium salt) (PSS) were alternatively
adsorbed on the surface of sulfur particles by
elec-trostatic interaction. The wall thickness
of sulfur particles can be well controlled by
adjusting the number of adsorption layer,
accompanied with a controllable permeability.
In present work, 10 bilayers of polymers were
assembled to obtain the dense sulfur shells.
Moreover, it has been found that the
crosslinking [24,32] and heat treatment

Fig. 1. The photos of pure sulfur

(yellow),
PANI-coated
sulfur
(green) and PPY-coated sulfur
(gray) composite materials asprepared. (For interpretation of the
references to color in this figure
legend, the reader is referred to
the web version of the article.)

occur, accompanied
by
reaction intermediates, the
soluble poly-sulfide anions.
The
existence
of
the
polysulfide can cause the
active mass loss of cathode
and anode, which are
attributed to polysul-fides
migration into the electrolyte
and finally precipitates on
the electrode surface. Now,
the as-prepared polymers
shells on the surface of
sulfur will effectively control
the slow release of sulfur
and polysulfide into the
electrolyte solutions. Finally,
to obtain a reversible
electrochemical reaction at
high current rates, conductive PANI and PPY are
assembled on the outer
surface
of
electrical
insulating sulfur particles by
electrostatic interaction with
oppo-sitely
charged
polyelectrolytes. As a result,
a novel sulfur composite
materials with an improved
electronic conductivity and
the dense shells were
obtained,
which
will
effectively
enhance
electrochem-ical
performance of lithium
sulfur battery.
Fig. 1 shows the photos
of pure sulfur (yellow), PANIcoated sulfur (green) and
PPY-coated sulfur (gray)
composite materials asprepared. In present study,

the synthesis of polyaniline is by oxidativepolyaniline due to its high

polymerization of aniline monomer with stability
at
room
ammonium peroxodisulfate as an oxidant.temperature and the fact
The components are both dissolved in 1 Mthat, upon doping with acid,
hydrochloric acid and slowly added to eachthe resulting emeraldine salt
other, consid-ering the exothermic reaction.form of polyaniline is
Polyaniline can be found in one of three electrically conducting [37].
idealized oxidation states showing different Leucoemeraldine
and
color and con-ductivity [36]. One is the fullypernigraniline
are
poor
reduced
state,
leucoemeraldine,
withconductors, even when
white/clear or colorless. Second is the fullydoping with an acid. Here,
oxidated state with imine links instead of the green sulfur powder can
amine links, pernigraniline, with blue/violet. be seen from the center
Another is the intermediate state, emeraldine, tube
(Fig.
1),
which
with green for the emeraldine salt and blue for demonstrated the highly
emeraldine base. Emeraldine form ofconductive emeraldine salt
polyaniline, often referred to as emeraldine by doped with acid was
base, is neutral, if doped it is calledsuccessfully obtained in
emeraldine salt, with the imine nitrogenssulfur materials. In the right
protonated by an acid. Emeraldine base is tube (Fig. 1), the gray sulfur
regarded as the most useful form of powder shows the presence

of PPY with well conductivity

in sulfur materials. For
comparison, pure sulfur
powder is shown in the left
tube (Fig. 1).
In the present work,
considering
the
better
utilization of sul-fur as
cathodes, commercial sulfur
powder with a large size
above 10 m was pre-treated
into a smaller size below 10
m
by
sieving
and
mechanical milling. Also, the
small sulfur particles are
more favorable to maintain
the intact encapsulation of
polymer after the

L. Duan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103

Fig. 2. SEM images of (a) pure sulfur particles before milling, (b) pure sulfur particles after milling, (c) (PAH/PSS) 10 PANI-coated
sulfur particles and (d) (PAH/PSS) 6 (PAH/PPY)4 - coated sulfur particles. The inset is higher magnification of a single sulfur particle.
Its EDX analysis is shown in the right of image.

polymers on the sulfur

following mulling for preparing sulfur cathodes. The particles. TEM image of
morphology of sulfur particles before and after coated a selected (PAH/PSS)10
by polymers was examined by both SEM and TEM. PANI-coated
sulfur
Fig. 2a and b shows the SEM morpholo-gies of sulfurparticles also displays
particles before and after milling, respectively. It can the successful coating
be seen that the size of sulfur particles after milled of
polymer
films
was obviously decreased and that the surface was (arrows), shown in Fig.
more glazed. Compared with pure sulfur particles, the 3. The inset shows its
sulfur particles layer-by-layer encapsu-lated by higher magnification.
polymers show a more dense and rough surface
To
know
the
structure, as shown in Fig. 2c and d for (PAH/PSS) 10electroactivity of PANI
PANI-coated sulfur and (PAH/PSS)6 (PAH/PPY)4after polymerized and
by
-coated sulfur, respectively. The differences of surface assembled
morphologies can be attributed to the well coat of electrostatic interaction
polyelectrolytes,
poly-mers on the surface of sulfur particles. The with
higher magnification of a single sulfur particle is the
provided in the inset. From its corresponding EDX
analysis, it further proved the existence of the

conductivity ( ) of asprepared
sulfur
composite
materials
was cal-culated from the
correlative
equation.
The electric resistivity ()
was first determined by
four-point
probe
technique
and
calculated according to
Eq. (1)
=0G

W
S D

where 0 is the measured

electric
resistivity,
G(W/S) is the correction coefficient of
sample thickness and

d
s

(1)

D(d/s) is the correction coefficient of sample shapePANI

forms
a
and measured position. The correction coefficient for continuous phase in the
G and D can be obtained from the reference data sulfur shell and even
according to the sample thickness, diameter andstill
maintain
its
measured posi-tion. Then, the conductivity ( ) wasconductive
property.
calculated from the reciprocal of resistivity (). As aThe
conductivity
result, for PANI-coated sulfur materials, thereached a high level
1
conductance is around 0.23 S cm , indicating thatsince PANI was doped

by hydrochloric acid in
the sulfur shell, which is
favorable to improve the
electrochemistry
performance of cathode

102

L. Duan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103

100

a
99
98

transmittance/%

96
95

2500

and (c) (PAH/PSS)6 (PAH/PPY)4

-coated sulfur composite materials.
Three samples show sim-ilar
patterns.

2000

1295
12441141

Fig. 4. XRD patterns of sulfur

powder
before
and
after
encapsulated
by
con-ductive
polymer: (a) pure sulfur, (b)
(PAH/PSS)10 PANI-coated sulfur

97

15661494

10

1500

1000
-1

500

1000
-1

500

Wavenumber (cm )
100

b
transmittance/%

98

92

a well electric conductivity of 0.006 S cm .

The interaction between PANI and sulfur
was investigated with X-ray diffraction (XRD)
patterns and Fourier transform infrared (FTIR)
spectroscopy. X-ray diffraction (XRD) patterns
of pure sulfur powder (PAH/PSS) 10 PANIcoated sulfur composite and (PAH/PSS) 6
(PAH/PPY)4 -coated sulfur composite are
shown in Fig. 3ac, respectively. The
characteristic diffraction peaks of sulfur

located at 22.9 and 27.4 , PANI and PPY at

26.0 . In Fig. 4, three samples show similar

XRD patterns with the diffraction peaks of
sulfur, PANI or PPY and no other impurity
peak. It demonstrated that, after layer-bylayer encapsulated by polyelectrolytes and
con-ductive polymers, the crystal structure of
sulfur still maintained its orthorhombic
corresponding to cyclooctasulfur molecule (S8
), and the encapsulation is only a physical
behavior and has no effect on sulfur.
FTIR spectra of PANI-coated sulfur and
PPY-coated sulfur is shown in Fig. 5a and b,
respectively. In Fig. 5a, the characteristic
1

Intensity/CP
S

peaks at 1566 and 1494 cm are due to the

stretching vibration of the quinoid ring and the
benzenoid ring, respectively [3840]. The

2500

11751043

1291

materials in lithiumsulfur battery. The PPYcoated sulfur cathode materials also possess

1458

94

1545

Fig. 3. TEM images of (PAH/PSS) 10 PANI-coated sulfur

particles. The inset is its higher magnification.

96

2000

1500

Wavenumber (cm )
Fig. 5. FTIR spectra of the powder:
(a)
(PAH/PSS)10
PANI-coated
sulfur
and
(b)
(PAH/PSS)6
(PAH/PPY)4 -coated sulfur.

bands at 1295 and 1244

1

cm can be assigned to C
H stretching vibration with
aromatic
conjugation
[41,42]. The absorption peak
1

near 1141 cm results from

the N Q N (Q denotes
quinoid
ring)
stretching
mode and is an indication of
electron delocalization in
PANI [43]. The results
further demonstrated that
the PANI poly-merized on
the surface of sulfur is the
conductive emeraldine salt,
and no chemical reaction
between
sulfur
and
polyaniline occurred for the
absorption,
which
was
achieved
mainly
by
electrostatic interaction. For
the PPY-coated sulfur, the
same conclusions were
obtained (Fig. 5b). The
characteristic bands of PPY
in sulfur com-posites were
consistent with references
[44,45]. The pyrrole ring
1
1
fundamental vibration are at 1545 cm and 1458 cm , the
1
1
in-plane vibration are at 1291 cm
and 1043 cm , and the C

C H
N

stretching vibration is at 1175 cm

4. Conclusions

heating treatment. The asprepared

sulfur
shells
possess a low permeability,
which is per-meable for very
small molecular weight of

In summary, a novel conductive polymer- Li+ and slowly or hardly for

coated sulfur compos-ite as cathode sulfur and polysulfide during
materials in lithiumsulfur batteries wascharge
and
discharge
successfully fabricated by a facile andprocess. The high electric
controllable
layer-by-layer
assemblyconductivity
of
sulfur
technique combined with crosslinking andcomposite materials further

pro-vides a well electron

conducting paths for the
rechargeability of lithium
sulfur battery. XRD patterns
and FTIR spectra reveal that
the encapsulation is only a
physical behavior and make
no effect for sulfur. The
present work may open a
new way to fabricate sulfur
cathode materials in lithium
battery.

L. Duan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103
cathode
material
for
rechargeable
lithium
batteries, Adv. Mater. 14 (13
14) (2002) 963965.

Acknowledgments
This work is financially supported by the
National Nature Sci-ence Foundation of
China (21103139).

[17]

M.M.
Sun,
S.C.
Zhang, T. Jiang, L. Zhang,
J.H. Yu, Nano-wire networks
of
sulfur-polypyrrole
composite cathode materials
for
rechargeable
lithium
batteries,
Electrochem.
Commun. 10 (2008) 1819
1822.

References

[1]

R.D. Rauh, K.M. Abraham, G.F. Pearson,

J.K. Surprenant, S.B. Brummer, A lithium/dissolved
sulfur battery with an organic electrolyte, J.
Electrochem. Soc. 126 (1979) 523527.

[18]

A. Gorkovenko, T.A.
Skotheim, Z.S. Xu, L.I.
Boguslavsky, Z.Y. Deng, S.P.
Mukher-jee,
Cathodes
comprising
electroactive
sulfur
materials
and
secondary batteries using
same. US Patent 6210831,
2001.

[2]

J. Shim, K.A. Striebel, E.J. Cairns, The

lithium/sulfur rechargeable cell, J. Elec-trochem.
Soc. 149 (2002) A1321A1325.

[3]

D. Marmorstein, T.H. Yu, K.A. Striebel, F.R.

McLarnon, J. Hou, E.J. Cairns, Elec-trochemical
performance of lithium/sulfur cells with three
different polymer electrolytes, J. Power Sources 89
(2000) 219226.

[19]

[4]

H. Yamin, E. Peled, Electrochemistry of a

nonaqueous lithium/sulfur cell, J. Power Sources 9
(1983) 281287.

[5]

H.S. Ryu, H.J. Ahn, K.W. Kim, J.H. Ahn, J.Y.

Lee, Discharge process of Li/PVdF/S cells at room
temperature, J. Power Sources 153 (2006) 360
364.

L. Duan, Q. He, K.W.

Wang, X.H. Yan, Y. Cui, H.
Mhwald, J.B. Li, ATP
biosynthe-sis catalyzed by
the F0 F1 -ATP synthase
assembled
in
polymer
microcapsules,
Angew.
Chem. Int. Ed. 46 (2007)
69967000.

[20]

[6]

J.A. Dean (Ed.), Langes Handbook of

Chemistry, 3rd ed., McGraw-Hill, New York, 1985,
pp. 35.

[7]

R.D. Rauh, F.S. Shuker, J.M. Marston, S.B.

Brummer, Formation of lithium poly-sulfides in
aprotic media, J. Inorg. Nucl. Chem. 39 (1977)
17611766.

[8]

S.E. Cheon, J.H. Cho, K.S. Ko, C.W. Kwon,

D.R. Chang, H.T. Kim, S.W. Kim, Structural factors
of sulfur cathodes with poly(ethylene oxide) binder
for per-formance of rechargeable lithium sulfur
batteries, J. Electrochem. Soc. 149 (2002) A1437
A1441.

[9]

[21]

K.W. Wang, Q. He,

X.H. Yan, Y. Cui, W. Qi, L.
Duan, J.B. Li, Encapsulated
photo-sensitive drugs by
biodegradable microcapsules
to incapacitate cancer cells,
J. Mater. Chem. 17 (2007)
40184021.

B.H. Jeon, J.H. Yeon, K.M. Kim, I.J. Chung,

Preparation and electrochemical prop-erties of lithium

sulfur polymer batteries, J. Power Sources 109 (2002)
8997.

[22]

[10]

S.E. Cheon, K.S. Ko, J.H. Cho, S.W. Kim,

E.Y. Chin, H.T. Kim, Rechargeable lithium sulfur
battery, J. Electrochem. Soc. 150 (2003) A796
A799.

[11]

Z.P. Guo, J.Z. Wang, H.K. Liu, S.X. Dou,

Study of silicon/polypyrrole composite as anode
materials for Li-ion batteries, J. Power Sources
146 (2005) 448451.

[12]

A. Du Pasquier, F. Orsini, A.S. Gozdz, J.M.

Tarascon, Electrochemical behaviour of LiMn2 O4
PPy composite cathodes in the 4-V region, J.
Power Sources 81 (1999) 607611.

[13]

B. Veeraraghavan, J. Paul, B. Haran, B.

Popoy, Study of polypyrrole graphite com-posite as
anode material for secondary lithium-ion batteries,
J. Power Sources 109 (2002) 377387.

[14]

J. Wang, J. Chen, K. Konstantinov, L. Zhao,

S.H. Ng, G.X. Wang, Z.P. Guo, H.K. Liu, Sulphurpolypyrrole composite positive electrode materials
for rechargeable lithium batteries, Electrochim.
Acta 51 (2006) 46344638.

[15]

A. Wu, H. Kolla, S.K. Manohar, Chemical

synthesis of highly conducting polypyr-role
nanofiber film, Macromolecules 38 (2005) 7873
7875.

[16]
novel

J.L. Wang, J. Yang, J.Y. Xie, N.X. Xu, A

conductive
polymer-sulfur
composite

S. Leporatti, C. Gao,
A. Voigt, E. Donath, H.
Mhwald,
Shrinking
of
ultrathin
polyelectrolyte
multilayer capsules upon
annealing: a confocal laser
scanning microscopy and
scanning force microscopy
study, Eur. Phys. J. E 5
(2001) 1320.

W.X. Song, Q. He, H.

Mhwald, Y. Yang, J.B. Li,
Smart
polyelectrolyte
microcap-sules as carriers for
water-soluble small molecular
drug, J. Control. Release 139
(2009) 160166.

103

[23]

A.H. Wang, C. Tao, Y.

Cui, L. Duan, Y. Yang, J.B. Li,
Assembly of envi-ronmental
sensitive microcapsules of
PNIPAAm and alginate acid
and their application in drug
release, J. Colloid Interface
Sci. 332 (2009) 271279.

[24]

L. Duan, Q. He, X.H.

Yan, Y. Cui, K.W. Wang, J.B.
Li, Hemoglobin protein hollow
shells fabricated through
covalent
layer-by-layer
assembly, Biochem. Biophys.
Res. Commun. 354 (2007)
357362.

[25]

L. Duan, W. Qi, X.H.

Yan, Q. He, Y. Cui, K.W.
Wang, D.X. Li, J.B. Li, Proton gradients produced by
glucose
oxidase
microcapsules
containing
motor F0 F1 -ATPase for
continuous ATP biosynthesis,
J. Phys. Chem. B 113 (2009)
395399.

[26]

Q. He, L. Duan, W. Qi,

K.W. Wang, Y. Cui, X.H. Yan,
J.B. Li, Microcapsules containing a biomolecular motor
for ATP biosynthesis, Adv.
Mater. 20 (2008) 29332937.

[27]

W. Qi, L. Duan, K.W.

Wang, X.H. Yan, Y. Cui, Q.
He, J.B. Li, Motor protein CF 0
F1 reconstituted in lipidcoated
hemoglobin
microcapsules
for
ATP
Synthesis, Adv. Mater. 20
(2008) 601605.

[28]

W. Qi, X.H. Yan, L.

Duan, Y. Cui, Y. Yang, J.B. Li,
Glucose-sensitive
microcapsules
from
glutaraldehyde cross-linked
hemoglobin
and
glucose
oxidase, Biomacro-molecules
10 (2009) 12121216.

[29]

Y. Jia, Y. Cui, J.B. Fei,

M.C. Du, L.R. Dai, J.B. Li, Y.
Yang,
Construction
and
evalua-tion of hemoglobinbased capsules as blood
substitutes,
Adv.
Funct.
Mater. 22 (2012) 14461453.

[30]

Y. Jia, J.B. Fei, Y. Cui,

Y. Yang, L. Gao, J.B. Li, pHresponsive
polysaccharide
microcapsules
through
covalent bonding assembly,
Chem. Commun. 47 (2011)
11751177.

[31]

J.B. Fei, Y. Cui, Q. He,

J.B. Li, Multilayer thin films:
sequential
assembly
of
nanocomposite materials, in:
G. Decher, J.B. Schlenoff
(Eds.), Assembly of Multilayer
Capsules
for
Drug
Encapsulation and Controlled
Release, 2nd ed., Wiley-VCH,
Weinheim, 2012, pp. 777
800.

[32]

W.J. Tong, C.Y. Gao,

H. Mhwald, Manipulating the
properties of polyelec-trolyte
microcapsules
by
glutaraldehyde cross-linking,
Chem. Mater. 17 (2005)

46104616.

[33]

Z.X. Wei, M.X. Wan, Hollow microspheres

of polyaniline synthesized by aniline emulsion
template, Adv. Mater. 14 (2002) 13141317.

[34]

R. Mueller, K. Khler, R. Weinkamer, G.B.

Sukhorukov, A. Fery, Melting of PDAD-MAC/PSS
capsules
investigated
with
AFM
force
spectroscopy, Macromolecules 38 (2005) 9766
9771.

[35]

K. Khler, G.B. Sukhorukov, Heat treatment

of polyelectrolyte multilayer cap-sules: a versatile
method for encapsulation, Adv. Funct. Mater. 17
(2007) 20532061.

[36]

W.J. Feast, J. Tsibouklis, K.L. Pouwer, L.

Groenendaal, E.W. Meijer, Synthesis, processing
and material properties of conjugated polymers,
Polymer 37 (1996) 50175047.

[37]

G. Tzamalis, N.A. Zaidi, A.P. Monkman,

Applicability of the localization-interaction model to
magnetoconductivity studies of polyaniline films at
the metal-insulator boundary, Phys. Rev. B 68
(2003) 245106245116.

[38]

X.Y. Shi, A.L. Briseno, R.J. Sanedrin, F.M.

Zhou, Formation of uniform

polyaniline thin shells and
hollow
capsules
using
polyelectrolyte-coated
microspheres as templates,
Macromolecules 36 (2003)
40934098.

[39]

H. Dong, S. Prasad, V.
Nyame,
W.E.
Jones,
Submicrometer
conducting
polyani-line tubes prepared
from polymer fiber templates,
Chem. Mater. 16 (2004) 371
373.

[40]

Y. Furukawa, F. Ueda,
Y. Hyodo, I. Harada, T.
Nakajima,
T.
Kawagoe,
Vibrational
spectra
and
structure
of
polyaniline,
Macromolecules 21 (1988)
12971305.

[41]

L.J. Pan, L. Pu, Y. Shi,

T. Sun, R. Zhang, Y.D. Zheng,
Hydrothermal synthesis of
polyaniline mesostructures,
Adv. Funct. Mater. 16 (2006)

12791288.

[42]

X.R. Zeng, T.M. Ko,

Structures and properties of
chemically reduced polyanilines, Polymer 39 (1998)
11871195.

[43]

Z.M.
Zhang,
J.Y.
Deng, J.Y. Shen, M.X. Wan,
Z.J. Chen, Chemical one step
method to prepare polyaniline
nanofibers
with
electromagnetic
function,
Macromol. Rapid Commun.
28 (2007) 585590.

[44]

J. Lei, W. Liang, C.R.

Martin, Infrared investigations
of
pristine,
doped
and
partially-doped
polypyrrole,
Synth. Met. 48 (1992) 301
312.

[45]

K. Cheah, M. Forsyth,
V.T. Truong, Ordering and
stability
in
conducting
polypyr-role, Synth. Met. 94
(1998) 215219.