*ORMOCERs as inorganicorganic electrolytes

for new solid state lithium batteries and

supercapacitors
M. Popall,
a
{ M. Andrei,
b
J. Kappel,
a
J. Kron,
a
K. Olma
a
and B. Olsowski
a
a
Fraunhofer-Institut fu r Silicatforschung, Neunerplatz 2, D-97082 Wu rzburg, Germany
b
Eniricerche, 1-20097 S. Donato Milanese, Milan, Italy
(Received 16 September 1996)
AbstractORMOCERs (ORganically MOdied CERamics) are inorganicorganic copolymers which are
synthesized as matrix for Li-ion conduction. The inorganic oxidic backbone of these materials results from
polycondensation of alkoxy compounds whereas the organic network is formed from reactive functional
groups R' of alkoxysilanes of the type R'Si(OR)
3
, or by co-polymerising reactive organic monomers with
reactive functionalized alkoxysilanes. Depending on the reactive organic functionalities and their thermal
and uv- initiated organic crosslinking reactions the materials were adapted to the needs of battery and
supercapacitor manufacturing. For ionic conductivity polyethers with dierent chainlengths and functiona-
lized (eg epoxy) termination sites were synthesized and attached to organically functionalized oxidic oligo-
mers. Conductivities of up to 10
4
O
1
cm
1
at room temperature (RT) were achieved without plasticizer.
The electrolytes form an amorphous network with conguration temperatures T
0
(according to Vogel
TammannFulcher) close to 808C, several degrees below the transformation temperature T
g
(measured by
DSC) in agreement with conventional conguration theory. The activation energies correlate favourably
with results for good polymer electrolytes. # 1998 Elsevier Science Ltd. All rights reserved
Key words: inorganicorganic copolymers, ORMOCERs, amorphous matrix, attachment of ethylene oxide
monomers, modular-design principle.
INTRODUCTION
Since the rst publications and fundamental investi-
gations of Wright [1] and Armand [2] in the early
eighties polymer ionic conductors became interest-
ing for applied research. Driving forces were on the
one hand the growing interest in low and medium
temperature fuel cells, on the other hand there is a
large market for environmentally friendly light-
weight rechargeable batteries and supercapacitors.
Polyethylene oxide (PEO), polyethylene imine,
polysuldes, etc. [3], were investigated, but PEO
still is the most commonly used material for hosting
lithium salts. As the conductivity at room tempera-
ture in pure PEO is limited by partial crystallization
various attempts were undertaken to achieve a
more amorphous and plasticized material. A large
number of investigations describe the use of comb-
branch polymers or copolymers with ionic conduc-
tivities up to 10
5
O
1
cm
1
[4]. Others in addition
modify the polymer electrolyte by using plasticizers
resulting in so-called gel-electrolytes [5]. Finally, as
an alternative, Armand et al. established plasticized
salts [6] eg lithium sulfonylimides like LiTFSI, to
achieve the plasticizing eect (disordering of the
crystalline structure of PEO) as well as better dis-
sociation of the salts.
Our attempts towards better conductivity are
based on amorphous networks formed from reac-
tive nano-sized functionalized oxidic oligomers.
Organic crosslinking reactions will result in inorga-
nicorganic hybrid materials.
These inorganicorganic copolymers
(ORMOCERs) in general are hybrid polymeric ma-
terials consisting of interconnected inorganic oxidic
Electrochimica Acta, Vol. 43, Nos 1011, pp. 11551161, 1998
# 1998 Published by Elsevier Science Ltd. All rights reserved
Printed in Great Britain
00134686/98 $19.00 +0.00 PII: S0013-4686(97)10014-7
*Registered trademark of Fraunhofer-Gesellschaft zur
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(FRG)
{Author to whom correspondence should be addressed.
1155
(Si, Al, Zr, etc.) and organic (polyethylene, poly-
(meth-)acrylate, polyethylene oxide, etc.) com-
ponents.
Synthesis is carried out via polycondensation
reactions (solgel processing) in combination with
organic crosslinking reactions of reactive functiona-
lized organosilanes. Depending on the chemical
composition and processing parameters, special
properties are available to meet the requirements
for the application technology [710].
Previous work on ORMOCERs as polymer
lithium ionic conductors is described [11, 12].
This short communication provides selected
aspects of the synthesis from a more applied point
of view. Some material properties and application
demands as well as the resulting conductivity will
be discussed. The use of these electrolytes in sec-
ondary lithium batteries, eg their stability versus
lithium and their use as binder for cathode ma-
terials, documented in long time cycling exper-
iments, are published by Skaarup et al. [13]. For
rst information on application in supercapacitors
see Ingram et al. [14].
EXPERIMENTAL
Synthesis of the functionalized oxidic backbone
2 mol 3-glycidyloxypropyltrimethoxysilane
(GLYMO) are hydrolyzed with 7.5 mol of water,
including dissolved NH
4
F (0.02 mol) as catalyst.
After 3 days at 508C the resulting emulsion is
extracted with CH
2
Cl
2
and dried.
The condensed GLYMO, dissolved in CH
2
Cl
2
is
cooled to 158C, 1 mol trivinylchlorosilane (VINYL)
is added dropwise and the mixture is stirred for
completion of the reaction. HCl, CH
2
Cl
2
and the
surplus of VINYL are then distilled o. After sev-
eral treatments with dry ethanol followed by distil-
lation (to remove HCl) the resulting resin is dried in
high vacuum. FTIR spectroscopy and Karl-
Fischer titration was used for detection of traces of
water and 0Si-OH.
Attachment of the epoxide monomers
The epoxy monomers RO(CH
2
CH
2
O)
5(6)
CH
2
CH(O)-CH
2
(EPOX5 and EPOX6) are attached
to the oligomers in 1:1 molar ratio corresponding
to GLYMO using catalysts for epoxy-polymeriz-
ation and temperatures up to 1008C.
In a similar way the diepoxide monomers
CH
2
-(O)CHCH
2
O(CH
2
CH
2
O)
1(3)
CH
2
CH (O)-CH
2
(EGDE and DIEPOX3) were reacted. The reactions
were monitored by FTIR spectroscopy and epox-
ide titration.
Establishing of the inorganicorganic Li-electrolyte
Lithium salts were dissolved in the dried functio-
nalized resins by stirring and initiators for thermal
or uv-curing were added. After casting in moulds
(diameter: 10 resp. 50 mm) the resin was applied to
uv-curing (high pressure mercury lamp) or heated in
an oven.
Dierential scanning calorimetry (DSC) investi-
gations were done in N
2
. Ac complex impedance
spectroscopy with stainless steel blocking electrodes
was used to measure the ionic conductivity of at
samples (diameter: 10 mm, height: ca. 0.5 mm, cov-
ered on both sides with graphite) at dierent tem-
peratures. In general after measurement of
conductivity at RT the samples were heated to
1008C in vacuum, held at those conditions over-
Fig. 1. Scheme for solgel synthesis of oligomers establish-
ing the inorganic oxidic backbone.
M. Popall et al. 1156
F
i
g
.
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.
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=
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X
5
a
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d
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=
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r
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P
O
X
6
)
.
ORMOCER's as inorganicorganic electrolytes 1157
F
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.
3
.
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.
M. Popall et al. 1158
night, then the temperature was decreased to RT
while measuring conductivity.
RESULTS AND DISCUSSION
Discussion of synthesis
Synthesis of the epoxide monomers. Mono-epoxide
monomers were synthesized by the functionalization
of an ethyleneglycol monoethyl or monomethy-
lether, having the required number of EO units,
with epichlorohydrine using the phase transfer cata-
lyst tetrabutylammonium hydrogensulfate, accord-
ing to [15, 16] in very high yields. As commercial
glycols are only available having up to 3 EO units,
longer EO chains were synthesized following the
route described in [16]. The synthesized monomers
were characterized by
1
H-,
13
C-NMR and FT-IR-
spectroscopy.
Synthesis of the functionalized oxidic backbone.
GLYMO was hydrolyzed and condensed (solgel
processing) at 508C by adding water using ammo-
niumuoride as catalyst. The resulting mixture (two
phases) was extracted or separated respectively. A
sol of nanosized oxidic particles functionalized with
epoxy groups results. According to FT-IR-spec-
troscopy there is still a small quantity of remaining
0Si-OH units. To remove them, they were reacted
with alkenyl chlorosilanes like VINYL (see Fig. 1).
Attachment of the epoxide monomers. After
extraction of HCl and evaporation of all solvents
and traces of HCl, the epoxide monomers EPOX5
and EPOX6 in 1:1 molar ratio corresponding to
GLYMO were attached as ion hosts by epoxy-poly-
merisation (see Fig. 2). As catalyst various lithium
compounds could be used. The use of lithium buty-
late will in addition lithiate all remaining alkyl-OH,
resulting from epoxypolymerisation. According to
FT-IR measurements and epoxide titration there is
nearly no remaining epoxy-functionality.
Establishing of the inorganicorganic Li-electro-
lyte. After careful drying of the resins of EO-func-
tionalized oligomers (monitored by FT-IR-
spectroscopy), lithium salts were dissolved (LiClO
4
,
other salts like LiBF
4
or LiSO
3
CF
3
were also
tested). After application as a coating or casting in
moulds the resins were thermally cured at 1008C
(see Fig. 3). Depending on the application as binder
for the cathode material or as separator in batteries
and supercapacitors, ethyleneoxide oligomers can
be added as plasticizer.
Material properties
The materials as resins are transparent and
slightly yellowish, caused by traces of impurities of
the epoxide monomer (not detectable with standard
methods). The resulting conducting membranes and
coatings are transparent, optically homogeneous,
slightly brownish and strongly hygroscopic.
According to X-ray diraction analysis the elctro-
lytes are amorphous.
Table 1 summarizes the values from the VTF
equation: This equation, which describes the depen-
dence of conductivity s on absolute temperature T:
s(T) = AT
1/2
exp[E
A
/R/(T T
0
)], (A is a constant
proportional to the number of ion carriers, E
A
is
the activation energy, R the gas constant and T
0
a
temperature close to T
g
), was tted to measured
values of temperature dependent conductivity.
Additional DSC measurements gave the values of
the transformation temperatures of the dierent
electrolytes. The T
0
and T
g
values are <08C and ac-
tivation energies in the range of 3 to 13
kJ K
1
mol
1
are typical for good polymer electro-
lytes and conform to lots of publications (see eg [3]
and [4]) the nal elasticity of the probes denes the
overall conductivity (electrodes/electrolyte withstand
included).
A closer look indicates some relationships
between conductivity and material structure caused
by dierent polycondensation and polymerisation
conditions: Systems 1 and 2 are identical in educt
composition. The only dierence is, that system 1 is
based on much smaller oligomers of condensed
GLYMO. The oligomer size clearly inuences the
Table 1.
Selected results from impedance spectroscopy and DSC measurements of lithium conducting ORMOCERs
ORMOCER
Sample no.
GLYMO
[wt.%]
VINYL
[wt.%]
Epoxy 6
[wt.%]
EGDE
[wt.%]
LiClO
4
[wt.%]
s
25
[O
1
cm
1
]
E
A
[kJK
1
mol
1
] T
0
[8C] T
g
[8C]
1 27.6 9.7 62.7 8.8 1.210
4
5.5 67 (60)
2 27.6 9.7 62.7 5.9 6.310
5
5.4 75 61
27.6 9.7 62.7 8.8 1.610
5
12.0 110 51
27.6 9.7 62.7 11.7 1.910
5
10.9 92 46
3 21.5 7.5 47.1 24.0 4.9 3.110
5
60
21.5 7.5 47.1 24.0 9.8 6.110
6
3.3 27
21.5 7.5 47.1 24.0 19.5 5.010
7
12.7 76
s: conductivity
E
A
: activation energy
T
0
: conguration temperature (close to T
g
)
T
g
: transformation temperature
ORMOCER's as inorganicorganic electrolytes 1159
rheology of the resins and therefore, the more
or less sterically hindered polymerisation of the
epoxy- and vinyl-functionalities. Random border
mechanisms [17] should of course inuence the ion
conductivity, based on the dierent oligomer sizes.
The less distinct dierence in conductivity despite
the drastic dierence in plasticity (oil = system 1 vs
hard gumlike membrane = system 2) could be a
hint but not more. The T
g
of system 1 should be
attributed more to some kind of relaxation of the
network than to a transformation.
To get more information about the best way of
attaching EO-units (as bridge between the oxidic
oligomers or as attached unit, free in rotation)
diepoxy endcapped EO-monomers like ethylenegly-
coldiglycidylether (EGDE) were chosen for copoly-
merisation with the monoepoxide EO-monomers
and the epoxy groups of condensed GLYMO in
system 3 (oligomer size similar to system 2). For
comparison the ``O''-concentration referring to the
organic network was kept constant compared to the
other electrolytes. As expected softer membranes
than in system 2 series result, caused by the plasti-
cizing polymerisation of EGDE and copolymerisa-
tion of EGDE with the monoepoxy EO-monomers.
The fact that despite this plasticizing eect the con-
ductivity is even lower could possibly be explained
by a lack of sterically unhindered EO-units close to
the oxidic backbone (in comparison to system 2).
This again would indicate that random border con-
ductivities close to the more inorganic ``oxidic''
areas will play an important role for the total con-
ductivity. The decrease in conductivity at high salt
concentrations conforms to the measured increase
of T
g
.
For more information about the inuence of
more or less mobile ion hosts the monoepoxide EO-
monomers were replaced by DIEPOX3, an EO-
monomer with 3 EO-units, both sides endcapped
with epoxide units. The plots in Fig. 4 show VTF
behaviour. The calculated curves t very well with
the experimental values. System 4 (composition, see
Fig. 4) having the same ``O'' concentration as the
others (referring to the organic network), shows
poor conductivity, conrming that EO-units ``brid-
ging'' inorganic areas are less promoting conduc-
tivity by stiening the whole network and enabling
only a sterically hindered handshaking mechanism
along the borders to the ``oxidic'' areas. Adding
PEO 400 (P400) or PEO 500 (P500) (concentration,
see Fig. 4) result in exible membranes with ionic
conductivities of up to 2.4 10
4
O
1
cm
1
at RT (see
Fig. 4).
CONCLUSION
This short communication demonstrates the syn-
thesis of inorganicorganic polymer electrolytes fol-
Fig. 4. VTF plots of systems 4 (O:Li = 20:1), ORMOCERs and PEO interpenetrated ORMOCERs: the dots represent
the measured values whereas the curves were calculated.
ORMOCER
GLYMO VINYL DIEPOX3 P500 P400 LiClO
4
s
25
Sample no. [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [O
1
cm
1
]
(a) 21.7 7.6 70.7 10.7 3.3010
9
(b) 17.4 6.1 56.5 20 10.6 2.2810
6
(c) 17.4 6.1 56.5 20 10.6 5.1510
6
(d) 47.5 16.7 35.8 8.4 9.0010
5
(e) 17.4 6.1 76.5 9.8 2.4010
4
M. Popall et al. 1160
lowing a modular-design principle. The inorganic
part not only guarantees the amorphous behaviour,
but the size of the oxidic oligomers and its kind of
EO-functionality have direct inuence on the con-
ductivity and the mechanical properties. All the sys-
tems discussed show ideal VTF behaviour and
dierent routes towards high conductivity are
described. Finally, the mechanical stability coupled
with easy processing as a coating indicates promis-
ing material properties.
ACKNOWLEDGEMENTS
This fundamental and applied research is part of a
Brite/EuRam project (BE 7251) funded by the
European Union. We wish further to thank the
technical sta at FhG-ISC and Eniricerche as well
as our project partners at Sonnenschein Lithium,
Thomson LCC, Universities of Denmark (S.
Skaarup et al.) and Scotland (M. Ingram et al.).
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ORMOCER's as inorganicorganic electrolytes 1161