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Lithium surface protection by polyacetylene in situ polymerization

Article  in  Synthetic Metals · May 2006

DOI: 10.1016/j.synthmet.2006.04.006

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 Synthetic Metals 156 (2006) 745–751

Lithium surface protection by polyacetylene in situ polymerization

D.G. Belov a , O.V. Yarmolenko b , A. Peng a , O.N. Efimov b,∗
a Industrial Technology Research Institute, 195 Chung Hsing Rd., Taiwan 310, ROC
b Institute of Problems of Chemical Physics Russian Academy of Sciences, 5 Acad. Semenov Avenue, Chernogolovka, Moscow Region 142432, Russia
Received 12 March 2006; received in revised form 11 April 2006; accepted 13 April 2006
Available online 26 May 2006

Abstract
Direct acetylene polymerization at ambient temperature on a Li metal surface and polyolefin separator with Ziegler–Natta catalyst was developed.
Thin conducting polyacetylene films with strong adhesion to Li or polyolefin surface was formed and studied by electrochemical methods. AC
impedance measurements and charge/discharge tests were applied for prepared coin cells with LiCoO2 as a cathode material in the presence of
1 M LiPF6 in dimethyl carbonate, ethylene carbonate, propylene carbonate (5:3:2 vol) electrolyte. Three kinds of polyolefins were used to prepare
composite separators with polyacetylene: polypropylene (PP), polyethylene (PE) and three-layer type: PP–PE–PP.
The polyacetylene film thickness on Li metal or polyolefin separator was easily controlled by catalyst concentration and polymerization time. It
was shown that high ionic conductivity (7.5 × 10−5 S cm−1 ) might be achieved due to higher porosity of a polyethylene separator. Li–polyacetylene
electrodes showed highest ionic conductivity and stability in charge/discharge tests.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Polyacetylene polymerization; Polyolefin/polyacetylene separator; Li surface protection; Impedance spectra

1. Introduction Although Li or Li–C electrodes are usually passivated by

The design of lithium-ion batteries, which use intercala-
tion electrodes, namely, a graphite anode and a lithiated metal
oxide (e.g. LiCoO2 ) cathode was an outstanding achievement
[1], which provided wide possibilities of the commercialization
of lithium batteries. Li-ion batteries are widely used in laptops
and cell phones and almost fully replaced conventional Ni–Cd
and metal-hydride batteries. Further progress could be achieved
due to the design of high-capacity batteries for electric vehicles
and buffer batteries for solar cells of geostationary satellites.
However, this requires thin electrodes and separators to lower
internal resistance of a battery. In this case lithium (alloy) anodes
seem to be quite suitable. Lithium possesses the highest nega-
tive potential equal to 3.045 V (in water) and the highest specific
characteristics, namely, 11.8 W h g−1 power and 3.86 A h g−1
capacity. Even the problems related to the changes in Li thick-
ness in charge/discharge cycles turn out to be not critical if a
separator or gel electrolyte possess high enough elasticity to
compensate these changes.
∗ Corresponding author. Tel.: +7 96 522 1887.
E-mail address: efimov@icp.ac.ru (O.N. Efimov).
surface films in optimized non-aqueous electrolyte solutions,
continuous reactions between active electrodes and organic elec-
trolytes remain unavoidable. Thereby, the cycle life of Li and
Li–C-based anodes is always limited by slow degradation of
both electrolyte solutions and the anode active mass.
Continuous studies of Li battery systems based on Li metal
anodes and commonly used non-aqueous electrolyte systems
revealed that heat evolution by such systems, which could lead to
explosion, was almost inevitable in abuse case, such as shorting,
overheating, overcharging, and overdischarging, etc.
Therefore, there is a problem of the design of a protection
coating on Li, which allows desolvated lithium cations to diffuse
fully or partially though it. Thus, is necessary to restrict the
access of reactive solvent molecules to the zone, where Li cations
are discharged and side reactions are realized, which result in
intense gas evolution and the formation of low-conducting alkyl
carbonates and Li carbonates (in the presence of water) [2]. As
a result, Li precipitate formed in battery charging consists of
encapsulated metal particles insulated from each other and from
leads.
In our previous study [3] we showed that PA film could be
synthesized directly on a Al–Mg substrate surface or mechani-
cally applied on it as a PA–separator composite film. PA coating

0379-6779/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2006.04.006
746 D.G. Belov et al. / Synthetic Metals 156 (2006) 745–751
provides significant increase of the rate of electrochemical Li
intercalation and the formation of the ␤-phase of Li/Al alloy,
and eliminates the direct electrode–electrolyte contact. This
minimizes gas evolution (as a result of electrolyte decompo-
sition) during the charge/discharge of Li battery and dendrite
growth.
Unfortunately, it is difficult to use free-standing PA films
since they are relatively easily oxidized by O2 and are rapidly
embrittled in a trans-form. Therefore, it becomes necessary to
improve physical–mechanical properties of PA and to enhance
its durability. For these purposes, the procedure of a porous film
filling with polyacetylene by acetylene polymerization in poly-
olefin film (separator) pores and on it surface was developed in
previous study [3].
Our new approach to protect Li metal surface in aprotic elec-
trolytes is direct acetylene polymerization (with Ziegler–Natta
catalyst): (a) on the Li metal surface and (b) on the polyolefin
separator film. Thus obtained thin PA film is very strongly adhe-
sive to both Li metal surface and polyolefin separator and appears
as an ion-conducting membrane impermeable for organic sol-
vents (such as PC or EC).
However, one of the causes of Li battery explosion could
be short circuit as a result of dendrite growth on a Li electrode
and through a separator. A well-known approach to decrease this
effect and prevent battery explosion is the use of shutdown sepa-
rators. Dendrite growth during cycling is significantly decreased
if a Li electrode is covered by a thin PA film. Additionally, one
could expect enhanced thermal stability of a composite separa-
tor in case of short circuit because of the presence of an infusible
PA layer [4].
PA can be reduced or oxidized electrochemically, these pro-
cesses being highly reversible. Therefore, PA electrodes can
find application in various electrochemical devices. For exam-
ple, rechargeable batteries were developed, in which polymer
electrodes of high capacity were used [4].
In 1979 of a PA film was anodically oxidized for the first time
in electrolytes containing I3 − , ClO4 − , and CF3 SO3 − anions
to form highly conducting state [5]. The electrochemical pro-
cess was reversible and was accompanied by the insertion of a
counter ion A− in doping (oxidation) and the removal in dedop-
ing (reduction) with a simultaneous transition of polyacetylene,
(CH)x , to a neutral non-conducting state:
(CH)x − xye− + xyA− ⇔ [CHy+ (A− )y ]x
However, PA can be easily intercalated by Li+ in cathodic polar-
ization, the polymer itself being negatively charged and becom-
ing highly conducting [3]:
(CH)x + xye− + xyLi+ ⇔ [CHy− (Li+ )y ]x
Table 1
Properties of Celgard separators
Number Separator Thickness (␮m) Melt temperature (◦ C)
1 PP 25 163
2 PE 21 135
3 PP/PE/PP 25 134/166
Li+ cations easily diffuse through a thin (5–10 ␮m) PA layer and
then are discharged on metallic Li surface:
Li+ + e ⇔ Limet
These electrode reactions are highly reversible, and on charging
a battery Li is easily ionized and diffuses through a PA coat-
ing to the interface as Li+ and then passes into the electrolyte.
At discharge state, Li+ diffuses back to an electrode through
PA (without solvent ions, X− ) and precipitates on the electrode
surface.
2. Experimental
2.1. Materials
High purity acetylene gas (99.9%) was used for acetylene
polymerization with additional purification column (to remove
moisture and acetone traces). Ziegler–Natta catalyst was pre-
pared from Ti(OBu)4 and Al(C2 H5 )3 , which were purchased
from Aldrich and used as it is. A separator film from Celgard®
Inc. (USA), polypropylene membrane, (PP), polyethylene mem-
brane, (PE) and trilayer membrane with one polyethylene layer
between two polypropylene layers (PP/PE/PP) (see Table 1)
was fabricated (a non-commercial product). All electrochem-
ical studies were carried out in a glove box under controlled
argon atmosphere. Commercial electrolyte (Sumitomo) con-
sisted of 1 M LiPF6 /DMC:EC:PC (5:3:2 vol) and was used for
electrochemical study of soft bag (“coffee bag”) and coin cell
samples.
2.2. Acetylene polymerization on the polyolefin
separator/membrane
The preparation of a bulk composite (separator/PA) involves
several stages and was described in detail in our previous study
[3]. The first stage is the preparation of a catalytic solution
[6], which contains Ti(OBu)4 and AlEt3 at a 1:4 molar ratio
and [Ti(OBu)4 ] = 0.5 g ml−1 , by stirring the components in dry
toluene in a flask blown with argon at room temperature for
30–60 min under 500–600 Torr. Then a microporous polymer
film was impregnated by a pre-evacuated catalyst (to remove part
of solvent), and acetylene polymerization started by acetylene
gas injection to the flask at room temperature for 10–60 min. A
possible mechanism of acetylene polymerization was described
in [7]. Then the obtained composite was washed with dry toluene
twice and continuously dried in vacuum. At the final stage the
PA film that appears as a black add-on on a porous polymer
matrix with two- or one-side coating depended on experimen-
tal procedure, was rolled directly on a Li electrode under small
Porosity (%) Pore size L × W (␮m × ␮m)
41 0.117 × 0.042
43 0.110 × 0.054
37 0.090 × 0.040
 D.G. Belov et al. / Synthetic Metals 156 (2006) 745–751
Fig. 1. Cross-section of separator/PA composite film (a) and Li metal/PA film (b) after acetylene polymerization.
pressure. The porous material with low density became denser
and quite well adhered to the metal surface. See Fig. 1(a).
2.3. Polymerization of PA on Li metal surface (Li/PA)
The preparation of Li/PA composite anode involves the same
stage of the preparation of a catalytic solution as described above
(Section 2.2). The difference is that a catalyst was aged at room
temperature and evacuated under dynamic pressure to acquire
desirable viscosity. Then the resulting catalytic solution was cast
(poured) on the freshly prepared Li foil surface with argon gas
flow and evacuated again to form more viscous solution. After
that acetylene gas was injected and polymerization of acetylene
on Li foil surface started immediately. The PA film thickness
on Li metal surface was easily controlled by reaction time and
pressure. See Fig. 1(b).
2.4. Cathode preparation
A positive electrode film was prepared from LiCoO2 mixed
with PVdF (polyvinylidene difluoride) (Atofina), graphite KS6
(Timcal) (91:3:6 wt.%) with N-methyl pyrrolidinone (NMP),
(solid/liquid = 1/0.37 weight parts). The resulting suspension
was well stirred to prepare a positive electrode material. This
mixture was coated at Al foil as current collector (20 ␮m thick-
ness) by Toray coater (Japan) and the resulting product was
dried in an oven at 120 ◦ C and pressed by a calendar machine
(to acquire appropriate electrode density).
2.5. Electrochemical measurements
AC impedance was performed on a Solartron SI 1287 Electro-
chemical Interface and a SI 1260 Impedance/Gain-Phase Ana-
lyzer, controlled by CorrWare and Zplot softwares. The EISs
were measured potentiostatically at cell open circuit voltage
(OCV) with AC oscillation of 10 mV amplitude at frequencies
from 100 kHz to 10 Hz. The stable OCV was obtained by cycling
the cell at constant current density of 0.1 mA cm−2 to the desir-
able value and then leaving it at open circuit for 10 min. The
collected EISs were fitted using ZView software. The samples
Table 2
Properties of composite “separator with PA” films after acetylene polymerization, washing and drying in vacuum
Number Composite film: separator/PA Thickness of film with PA layer (␮m)
1 PP–PA 28
2 PE–PA 27
3 PP/PE/PP–PA 31
747
for tests were made in a soft bag (Al laminated foil) and in coin
cell.
Morphology of polymer membranes was examined by scan-
ning electron microscopy (SEM, JEOL JSM-840) at 5 kV after
being sputtered with gold at 10 mA for 1 min.
Electrical tests were performed on a Maccor 4000 tester.
3. Results and discussion
In this study we extended the amount of separator films to
three kinds (Celgard® not regular product) (Table 1). For every
kind of a separator film there are differences in porosity and
pore structure as well as thickness. Acetylene polymerization
was performed in similar conditions for each type of a sep-
arator and only on one side of a separator. The data for the
samples before and after acetylene polymerization are presented
in Tables 1 and 2, and SEM microphotographs of the surface
view of films (Fig. 2(a)–(c)) and edge of films (Fig. 3(a)–(c)).
The average thickness increase after polymerization is ∼5 ␮m.
As seen from Table 1 and Fig. 3, the PP/PE/PP separator film
has lowest porosity. In this case PA film is located only on the
separator surface with very poor adhesion (see Fig. 3(c)). On the
contrary, PE film has highest porosity and, as a result, viscous
catalytic solution well impregnates a separator film, and after
polymerization PA film has very strong adhesion to its surface
(see SEM Fig. 3(b)). As a result, new material has higher ionic
conductivity (Fig. 4).
The AC impedance spectra and an equivalent circuit of
PP and PE separators with PA add-on and PA on Li metal
surface/LiCoO2 cells are shown in Fig. 5. Three formation cycles
were realized and then the cells were charged to E ≈ 4.1 V.
All AC impedance spectra consist of a depressed semicircle
in the high-to-medium frequency range and a lightly curved line
in the low frequency range. Different shapes appear only for the
Li/PP separator/Li cell, which consist of two equal semicircles
in the high-to-low frequency range (Fig. 5).
Such impedance spectra can be easily fitted with an equiv-
alent circuit shown in Fig. 6(a) and (b). In this circuit Rel is
attributed to the resistance of liquid electrolyte and corresponds
to the high frequency intercept at the real axis. A parallel sub-
Thickness of PA layer (␮m) Content of PA (wt.%)
3 15
6 21
6 13
748 D.G. Belov et al. / Synthetic Metals 156 (2006) 745–751

Fig. 2. (a) SEM photographs of the surface view of pure PP separator (Celgard® ) (1) MAG = ×3000 and after acetylene polymerization surface view PP–PA (2)
MAG = ×8000. (b) SEM photographs of the surface view pure PE separator (Celgard® ) (1) MAG = ×3000 and after acetylene polymerization surface view PE–PA
(2) MAG = ×7000. (c) SEM photograph of the surface view of pure PP/PE/PP separator (Celgard® ) (1) and after acetylene polymerization surface view PP/PE/PP–PA
(2) MAG = ×7000.

circuit comprising resistor Rct , charge transfer resistance and
a constant-phase-angle element CPE1 is used to simulate the
depressed semicircle.
After the formation (E ≈ 4.1 V) each spectrum for
Li/PP–PA/LiCoO2 and Li/PE–PA/LiCoO2 samples displays two
arcs. The first, at middle frequency, can be associated with
an ionic conducting surface layer, which grows on the Li sur-
face. The low frequency semicircle is related to charge transfer
between the surface layer and the electrode. This behavior can
be ascribed to an initially poor interfacial contact between the
PA polymer film on a separator and the Li electrode. Since the
total interfacial resistance is shown to be much greater than the
electrolyte resistance, it is of crucial importance to minimize
resistance for practical application. The Warburg line related
to the diffusion of Li-ions in cathode material completes the
AC impedance diagram. This indicates that kinetics of the elec-
trochemical intercalation process becomes diffusion-controlled.
However, the AC impedance curve of the Li–PA electrode has
a very small arc at high frequency (Fig. 5(b)) attributed to a
very good interface between Li metal – PA film – separator
and the similar behavior of the Warburg line at the high fre-
quency range. The depressed semicircle could be associated
with charge transfer process occurring at Li/electrolyte and
LiCoO2 /electrolyte interfaces. In case of the sample with the
PE (PP)—PA–separator, Rct and CPE1 are almost equal to both
contributed interfaces but in case of Li–PA electrode the con-
 D.G. Belov et al. / Synthetic Metals 156 (2006) 745–751 749

Fig. 3. (a) SEM of edge of PP–PA composite film, upper layer is PA film. MAG = ×3000. (b) SEM of edge of PE–PA composite film, upper layer is PA film.
MAG = ×8000. (c) SEM of edge of PP/PE/PP–PA composite film, lower layer is PA film. MAG = ×2000.

tribution of the Li/electrolyte interface is very small and the
semicircle has a very small diameter (∼40
). Charge trans-
fer resistance, Rct , is the major part of cell impedance, while
CPE1 is closely related to the electrical double layer capacitor.
In addition, another CPE element, i.e. CPE2, is used in the equiv-
alent circuit to simulate the low frequency straight line. This is
Fig. 4. Ionic conductivity of the composite film (separator–PA) with elec-
trolyte solution: 1 M LiPF6 /DMC:EC:PC (5:3:2 vol) in coin cell 2325
(Li/separator–PA/LiCoO2 ); 10–105 Hz frequency.
actually Warburg-type impedance, which reflects solid-state Li
ion diffusion and AC accumulation of lithium in the electrode
at very low frequency. The data of fitting with Zview software
(non-linear-least-squares-regression) are shown in Table 3. It
is obviously that charge transfer resistance in the Li–PA/PP
separator/LiCoO2 cell is significantly less than that in any other
combinations. This could be a result of a Li–PA/electrolyte
two-way interaction (cooperation), i.e. PA is an electronically
conducting polymer (ECP), in which the doping–dedoping pro-
cess involves injection-removal of electrons in the polymer film
balanced by counter-ion diffusion from-to the electrolyte. The
model for thin homogeneous films of intercalation materials, in
which lithium injection and diffusion was developed by Ho et
al. [8], and independently, by Glarum and Marshall [9]. How-
ever, it could be a result of Li metal surface modification during
acetylene polymerization by the Ziegler–Natta catalyst.
The sample with a Li/PP separator/Li has two large and
almost equal arcs at high and low frequency regions. This behav-
ior can be attributed to the reaction of electrolyte with both Li
surface and LiCoO2 electrodes.
The charge/discharge curves (1–5 cycles) of Li–PA/PP
separator/LiCoO2 cell are presented in Fig. 7. A comparative
analysis of charge/discharge characteristics shows that the pres-
750 D.G. Belov et al. / Synthetic Metals 156 (2006) 745–751

Fig. 5. Impedance spectra of coin cell Li/sample separator/LiCoO2 with electrolyte solution: 1 M LiPF6 /DMC:EC:PC (5:3:2 vol); 105 –10 Hz frequency after three
formation cycles. E = 4.1.

Fig. 6. Equivalent circuit used for fitting the impedance spectrum shown in Fig. 5 and results of fitting in Table 3: (a) for Li/PP separator/LiCoO2 cell with 1 M
LiPF6 /DMC:EC:PC (5:3:2 vol) electrolyte; (b) for other cells.

Table 3
Fitting results of the AC impedance spectra (Fig. 5) with equivalent circuits shown in Fig. 6(a) and (b) of the coin cell 2325 with different separator combinations
10–105 Hz frequency
Elements of equivalent circuit Li/PP/LiCoO2 Li–PA/PP/LiCoO2 Li/PE–PA/LiCoO2 Li/PP–PA/LiCoO2

Rel 25 3 15 5.8
Rct 380 40 215 175
CPE1 5 × 10−4 4.3 × 10−4 1.5 × 10−4 8 × 10−6
CPE2 0.035 0.001 0.008 0.035
R1 295 – – –

Fig. 7. Charge/discharge curves of coin cell Li–PA/PP separator/LiCoO2 with 1 M LiPF6 /DMC:EC:PC (5:3:2 vol) electrolyte at 0.2 C rate at 1st and 5th cycle.
 D.G. Belov et al. / Synthetic Metals 156 (2006) 745–751
ence of the PA coating does not deteriorate electrochemical
properties of metallic lithium. Therefore, composite Li–PA elec-
trodes showed stability in charge/discharge tests.
4. Conclusion
Extended studies of acetylene polymerization on a separator
(microporous membrane) were performed and a new composite
material was tested by SEM and AC impedance. Three types
of the separator (Celgard® : PE, PP and PP/PE/PP) were used.
The quality of a composite film depends on separator poros-
ity and thickness. Obviously, higher porosity of the separator
(PE > PP > PP/PE/PP) results in better PA–separator adhesion
and lower AC impedance of the composite film.
The new composite material—Li–PA was obtained by direct
acetylene polymerization on a lithium metal surface. Thin PA
film well covered and chemically adhered to a Li metal surface.
This method provides some Li metal surface modification by
the Ziegler–Natta catalyst. Thin PA film on a Li metal surface
or a polyolefin separator and chemically modified Li electrode
View publication stats
751
surface effectively protect Li surface during charge/discharge
cycling and improve cell impedance. PA can improve safety of
Li battery as well.
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