Sohd State lomcs 36 (1989) 165-169

North-Holland, Amsterdam

INCREASING THE CONDUCTIVITY OF POLYMER SOLID ELECTROLYTES: A REVIEW

J P R Z Y L U S K I and W W I E C Z O R E K
Instttute of Sohd State Technology, Warsaw Umverstty of Technology, ul Noakowsktego3, 00-664, Warszawa,Poland

Received 18 July 1988, accepted for pubhcatlon 21 December 1988

The a~m of this work is to present various methods whachwere mvesUgatedto ancreasethe conduct~vityof polymer electrolytes
Modlficatmns of crystalline structure of PEO-based electrolytes by copolymenzatton with amorphousazlngagents, adding ceramac
powders and forming haghlyamorphous blend type mixtures or grafted copolymers wall be described The revaew as based on our
own results as well as the reports of other authors

1. Introduction ~X
10
Polymer electrolytes became materials o f consid- 300 K 338 K V V
I v V~V
erable interest due to the wide range o f their possible V
08
apphcatlons Ionic nature o f the complexes between
poly (ethylene oxide) - PEO and alkali metal salts x x x~ r
x
was first reported by Wright [ 1,2 ] and more care- O~ x
x
x
fully studied by A r m a n d and coworkers [3 ] Al-
though solid electrolytes based on PEO, alkali metal 0,4
salts complexes, exhibit rather good mechanical
properties, compatibility with alkah metal electrodes
and relatively simple preparation, their significantly Q2 oooooooI ,o,
~VVV V 0 0
low ionic conductivity at ambient temperature con- I f o Oo o
siderably hmlts their usage The increase o f the ionic i 1 I I t I I

conductivity o f polymer electrolytes IS connected wRh 273 373 T [K]

changes o f the phase structure o f these materials
Berthler et a l [ 4 ] established that ionic conductiv- Fig 1 FracUon of protons belongmg to ( ~7) amorphous phase,
( ) pure crystalline PEO, ( ) crystalline complex phase [ 5 ]
ity in polymer electrolytes is associated with the
amorphous phase o f the studied samples PEO based
types o f polymers, exhibiting properties comparable
polymer solid electrolytes have rather comphcated
or even better than o f PEO systems were also in-
structure at room temperature as can be seen In fig
vestigated All these studies were s u m m a n z e d and
l [ 5 ] The contribution o f the amorphous phase into
properly explained by Vincent [ 6 ] and A r m a n d [ 7 ]
this structure is rather low Following Berthler's as-
In our paper some new methods which offer the pos-
sumptions a n u m b e r o f methods to produce polymer
slbihty to prepare highly conductive room temper-
electrolytes in a stable amorphous form were devel-
ature polymer solid electrolytes are reviewed
oped Several routes leading to modifications o f the
crystalline structure o f PEO based systems like cross-
linking, utihzing comb-like polymers, different ways
of sample preparation, complexlng with organic salts 2. H i g h molecular weight P E O copolymers
to lower the melting point o f the eutectlc, were ap-
plied Complexes formed by metal salts with other An interesting method of producing highly amor-

0 167-2738/89/$ 03 50 Elsevier Science Publishers B V

( North-Holland Physics Pubhshlng Division )
166 J Przfluskl, W Wleczorek / Conducttvtty of polymer sohd electrolytes

phous polymeric electrolytes is to prepare PEO co-

polymers Several reports on high molecular weight Log B IS em"1]
PEO copolymers are known [ 8-12 ] Nichols and co-
-4
workers [ 9 ] used oxymethylene linked PEO as a ma-
terial for solid electrolytes. Product was obtained
from CHEBr2 and PEG - poly(ethylene glycol), by -5
Wllhamson reaction Glass transition temperature
o
T g = - 65C of such obtained copolymer was com- -6
parable to that of pure PEO Ionic conductivity of x
polymer complex with L1CF3SO3 varrled from o
-7:
5 l0 -5 S/cm at 25 C to 10 -4 S/cm at about 100C X
(
Linden and Owen [ 1 l, 12 ] examined electrical prop-
erties of highly amorphous oxymethylene-oxyethy- -8
lene copolymer-based polymer electrolyte, but they
did not report on ionic conductivity of the studied i

material Armand [8 ] reviewed P E O - P P O copoly- 0 20

mer and also other system obtained by copolymer-
~zation of ethylene oxide with methyl-glicyd ether
For copolymerizatlon reaction aluminum-organic
catalysts were used Molecular weight of such pre-
pared polymers was about 105g/mol Room-temper-
ature ionic conductivity for alkali metal salts com-
plexes with oxyethylene-methyl glicyd ether
copolymer was equal to 3 l0 -5 S / c m
Results of the study of P E O - P P O copolymers were
also given by Passmieml et al [ 10 ] Their materials
were synthetized by using organotm-phosphate or
Teyssle-Osgan catalyst Molecular weight changed
from 5 103 to 7 104 g / m o l with changing of E O /
PO ratio in the reaction m~xture The best value of
the conductivity for the samples containing LICIO4
was obtained for E O / P O = 1
Some experiments with polymer electrolyte films
based on P E O - P P O copolymers [ 13] were carried
out in our group These experiments with NaI-doped
polymer electrolytes are m a good correlation with
those described above Both the conductivityand the
molecular weight of the obtained copolymer depend
strongly on molar fraction of EO m the reaction mix-
ture and decreased for high PO concentrations The
best value of the ionic conductivity 2 6 10-s S / c m
at 25 C was measured for sample containing 60% of
PEO Molecular weight increased from about 104g/
mol for pure PPO to 105g/mol for high EO concen-
trations Fig 2 shows the comparison of our con-
ductivIty results with those obtained by the Finnish
group The reason of the high increase of the con-
ductivity is probably due to a random distribution
' '4'0 . 60
. . . 80 (%]
EO
Fig 2 Roomtemperaturebulk conducUvltyfor" ( X ) PEO-PPO-
L1CIO4polymer electrolyte [ l 0 ], ( O ) PEO-PPO-NaI polymer
electrolyte [ 13]
of EO umts m a polymer chain Such structure was
checked by N M R measurements Highly amorphous
character of prepared copolymers was confirmed by
X-ray diffraction experiments There were no peaks
characteristic of the crystalhne structure of PEO on
X-ray dlffractograms Although polymer solid elec-
trolytes based on high molecular weight P E O - P P O
copolymers exhibit high RT ionic conductivity their
mechanical properties are poor This problem could
be overcome by increase of a molecular weight to the
range 105g/mol
3. Polymer blends and grafted copolymers
Another possibility of preparing highly conductive
polymer electrolytes is to synthesize polymer blends
or grafted copolymers To be successful in investi-
gations of polymer blends at least three main facts
connected with the plasticizer used should be con-
sidered [ 14 ]
( 1 ) plasticizer has to be completely miscible with
amorphous phase of main polymer,
(2) in the studied temperature range its vapour
pressure should be low,
(3) stablhty against electrode materials should be
high enough
 J Przyluskt, W Wwczorek / Conductivity of polymer sohd electrolytes
Kelly et al [ 14,15 ] examined propylene carbon-
ate and low molecular weight PEG as plastlclzers for
PEO based electrolytes Experiments with PC have
been dropped because of its high vapour pressure
Also PEG ( M W = 4 0 0 ) could not be used as a plas-
ticizer due to high lnterfaclal resistivity in contact
with lithium electrode and only results of apphca-
tion of &methyl poly(ethylene glycol) PEDMGE,
were promising enough Conductivity for systems
containing L1CF3SO3 rose to the value 10 -5 S / c m
and l0 -4 S / c m at 30 and 40C respectively Peak of
a crystalline complex phase was absent on the DSC
traces These facts can be explained by dissolution of
the crystalline phases in the plasUclzer This led to
lowering crystalhnity of the sample and hence to m-
crease of the conductlvaty values
Rmtman et al [ 16] showed high conductivity
(2 5 10 -4 S/cm at 40C) for systems based on poly
(vinyl carbonate) PVC, with crown ethers additives
Polymers containing 12-crown-4 ether which is lith-
ium specific were studied The best results were ob-
tained for [PVC] / [crown ether] ratio 1 1 The
mechanism of conduction is probably similar to that
observed in biological lonophores membranes
The role of polystyrene ad&tlves to the PEO-based
electrolytes was described by Gray et a l [ 17 ] Me-
chanical properties of polymer films were improved
hut the addition of polystyrene caused little decrease
of the conductivity especially at the low temperature
region In the case of the samples prepared by ther-
mal polymerization of styrene in the presence of PEO
and a salt, a fraction of a grafted copolymer was ob-
tained Conductivity varied in the range 10-6-10 -5
S/cm at moderate temperatures Kobayashi and co-
workers [ 18 ] blended low molecular weight PEO
with PMAA, (polymethacryhc a o d ) Reported con-
ductlvlty was l 0 -6 S / c m at 25C In our laboratory
some experiments with P E O - P M M A [poly(methyl
methacrylate) ] blends and grafted copolymers have
been carried out [ 19 ] By blending these two poly-
mers the conducUvRy has been improved slightly but
the real breakthrough was made in the case of grafted
copolymers Conductivmes of about 10 -5 S / c m at
20C were measured Our assumptions that grafted
phase is responsible for so high value of ionic con-
ductivlty is in good agreement with considerations
described by other authors [ 17] Highly mhomo-
genous mixture consisted of at least three phases
167
namely pure PEO, pure PMMA, and the grafted
phase was formed dunng the reaction However, the
separation of the grafted copolymer is a serious
problem
Other results concerning polymer blends were re-
ported by Le Mehaute and coworkers [20] Small
amount of styrene terminated macromer, prepared
according to the method described by Revflion [ 21 ],
has been added to a PEO-based electrolyte together
with a buta&ene-styrene copolymer The resulting
mixture of these compounds was cross-hnked by X-
ray irradiation or by treatment at a temperature of
about 150C Stable amorphous phase was formed
Conductivity for such long-time stable polymer elec-
trolyte was equal 2 1 0 -4 S / c m near room
temperature
4. Polymer solid electrolytes with ceramic additives
New method of introducing inert ceramic grams
into polymer matrix to enhance ionic conductivity
was developed by two groups [22-24 ] Earlier Wes-
ton and Steele [25] have added a-Al2Oa fillers to
polymer electrolytes mainly to improve their me-
chanical properties Small increase of the conductiv-
ity for addition of a-A1203 (grain size 40 I~m) up to
10V/v was found For higher concentrations of a ce-
ramic powder the conductivity dropped down rap-
idly due to the formation of low conducting ceramic
regtons in a polymer matrix He and coworkers [22 ]
used T-A1203 which was characterized by grain size
in the range 0 3-1 p.m They concluded that con-
ductlvlty is strongly dependent on the particle size
used The effect observed was similar to that de-
scribed by authors who had studied influence of a-
A1203 particles on the conductivity of LII solid elec-
trolyte For small diameters of T-AI203 grams the
conductivity of P E O - N a S C N electrolyte increased
about five times in comparison to the samples not
containing ceramic powder and reached the value
1 2X 10 - s S/cm at 30C Increase of the conductiv-
ity was observed up to 30W/w of T-A1203 The studies
on addmon of different aluminum oxides (a, ~,) have
been undertaken in our group [23,24] We have es-
tablished that processes taking place during sample
preparation lead to serious changes in the structure
of the studied polymer electrolytes Fig 3 presents
168 J Przytuskl, W Wteczorek I Conductivity of polymer sohd electrolytes

dltlOn of NASICON powder caused a decrease of

' Log 6 Is cm -1] crystalline phases of polymer electrolyte [ 24 ]. Influ-
-2
ence of the added NASICON was very similar to this
-3
reported for samples with aluminum oxide derlva-
o x
o o~
x
uves Direct conducUon through NASICON grams
oo x o x
could not take place probably due to the formation
-4 o x
x
o
of a passlvatlng layer on a surface of NASICON par-
oo
)to
ucles Occurence of such a layer is suggested by an
-5 x
oo
o o extremely high phase boundary resistance The best
, , ~
values of conductlvmes measured for our samples
' 2'8 ' 3'0 ' 3'2 3/, [K -1 were about 10 -5 S / c m near RT Systems described
IO001T
above are interesting due to the fact that m contrast
Fig 3 Bulk conductivity versus remprocal temperature for to polymer electrolytes the crystalhne ceramic elec-
( X ) PEO-LICIO4 - 10% o.-A1203 (grain sizes 40 ~tm ) [ 25 ], ( ) trolytes have cauon transport number equal to l and
PEO NaSCN - 30% "/-AI203 (gram sizes 0 7 Ixm) [22], ( ) thereby prevent the formation of concentration gra-
PEO-NaI - 10% 0-A1203 (gram sizes 2 btm) [23]
dient that may lead to h m m n g current effects

the comparison of our results and those reported by

He and the English group 5. Conclusions
Possibility of utlhzlng highly conductive ceramic
solid electrolytes m mixed phase sohd polymer elec- Several methods which lead to an increase of the
trolytes system were first proposed by Stevens et al. RT Ionic conductivity of polymer electrolytes were
[26 ] The authors have investigated the conductiv- reviewed Although there are systems which have
ity and the phase structure of PEO-MAg415 (M = Rb, ionic conductivity of about l0 -4 S / c m at or near RT,
LI, K ) mixed-phase electrolytes R o o m temperature the investigations of new systems are still in prog-
conductivity for O / M = 1 ratio vaned from l0 -4 S/ ress It seems that the study of comb-branched poly-
cm for LI to 2 l0 -3 S / c m for Rb atoms containing mers, high molecular weight copolymers, polymer
sdver electrolyte and was far below values reported blends and grafted copolymers is the most promising
for MAg415 ceramic electrolytes under the same con-
ditions The results were m good agreement with the-
oreUcal values of the conducuvity calculated from Acknowledgement
percolation theory PercolaUon phenomena occured
for the O / M raUo above 0 2 Slmdar observauons The authors wish to thank Dr J Plocharskl for
were reviewed by Skaarup et al [27] for the system helpful discussion This work was financially sup-
based on LI3N and (PEO)~oLICFaSO3 electrolytes ported by Polish Mlnlstery of Education under
Conducuvlty was equal to 10 -5 S / c m at RT but C P B P 01 15 research programme
dropped down rapidly for L13N volume concentra-
tions below 85% The samples for conductivity mea-
surements were prepared by the hot-pressing tech- References
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