Beruflich Dokumente
Kultur Dokumente
North-Holland, Amsterdam
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
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
Kelly et al [ 14,15 ] examined propylene carbon- namely pure PEO, pure PMMA, and the grafted
ate and low molecular weight PEG as plastlclzers for phase was formed dunng the reaction However, the
PEO based electrolytes Experiments with PC have separation of the grafted copolymer is a serious
been dropped because of its high vapour pressure problem
Also PEG ( M W = 4 0 0 ) could not be used as a plas- Other results concerning polymer blends were re-
ticizer due to high lnterfaclal resistivity in contact ported by Le Mehaute and coworkers [20] Small
with lithium electrode and only results of apphca- amount of styrene terminated macromer, prepared
tion of &methyl poly(ethylene glycol) PEDMGE, according to the method described by Revflion [ 21 ],
were promising enough Conductivity for systems has been added to a PEO-based electrolyte together
containing L1CF3SO3 rose to the value 10 -5 S / c m with a buta&ene-styrene copolymer The resulting
and l0 -4 S / c m at 30 and 40C respectively Peak of mixture of these compounds was cross-hnked by X-
a crystalline complex phase was absent on the DSC ray irradiation or by treatment at a temperature of
traces These facts can be explained by dissolution of about 150C Stable amorphous phase was formed
the crystalline phases in the plasUclzer This led to Conductivity for such long-time stable polymer elec-
lowering crystalhnity of the sample and hence to m- trolyte was equal 2 1 0 -4 S / c m near room
crease of the conductlvaty values temperature
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 4. Polymer solid electrolytes with ceramic additives
Polymers containing 12-crown-4 ether which is lith-
ium specific were studied The best results were ob- New method of introducing inert ceramic grams
tained for [PVC] / [crown ether] ratio 1 1 The into polymer matrix to enhance ionic conductivity
mechanism of conduction is probably similar to that was developed by two groups [22-24 ] Earlier Wes-
observed in biological lonophores membranes ton and Steele [25] have added a-Al2Oa fillers to
The role of polystyrene ad&tlves to the PEO-based polymer electrolytes mainly to improve their me-
electrolytes was described by Gray et a l [ 17 ] Me- chanical properties Small increase of the conductiv-
chanical properties of polymer films were improved ity for addition of a-A1203 (grain size 40 I~m) up to
hut the addition of polystyrene caused little decrease 10V/v was found For higher concentrations of a ce-
of the conductivity especially at the low temperature ramic powder the conductivity dropped down rap-
region In the case of the samples prepared by ther- idly due to the formation of low conducting ceramic
mal polymerization of styrene in the presence of PEO regtons in a polymer matrix He and coworkers [22 ]
and a salt, a fraction of a grafted copolymer was ob- used T-A1203 which was characterized by grain size
tained Conductivity varied in the range 10-6-10 -5 in the range 0 3-1 p.m They concluded that con-
S/cm at moderate temperatures Kobayashi and co- ductlvlty is strongly dependent on the particle size
workers [ 18 ] blended low molecular weight PEO used The effect observed was similar to that de-
with PMAA, (polymethacryhc a o d ) Reported con- scribed by authors who had studied influence of a-
ductlvlty was l 0 -6 S / c m at 25C In our laboratory A1203 particles on the conductivity of LII solid elec-
some experiments with P E O - P M M A [poly(methyl trolyte For small diameters of T-AI203 grams the
methacrylate) ] blends and grafted copolymers have conductivity of P E O - N a S C N electrolyte increased
been carried out [ 19 ] By blending these two poly- about five times in comparison to the samples not
mers the conducUvRy has been improved slightly but containing ceramic powder and reached the value
the real breakthrough was made in the case of grafted 1 2X 10 - s S/cm at 30C Increase of the conductiv-
copolymers Conductivmes of about 10 -5 S / c m at ity was observed up to 30W/w of T-A1203 The studies
20C were measured Our assumptions that grafted on addmon of different aluminum oxides (a, ~,) have
phase is responsible for so high value of ionic con- been undertaken in our group [23,24] We have es-
ductivlty is in good agreement with considerations tablished that processes taking place during sample
described by other authors [ 17] Highly mhomo- preparation lead to serious changes in the structure
genous mixture consisted of at least three phases of the studied polymer electrolytes Fig 3 presents
168 J Przytuskl, W Wteczorek I Conductivity of polymer sohd electrolytes
[6] C A Vincent, Prog Sohd State Chem 17 (1987) 145 [ 18 ] E Tsuchlda, H Ohmo, K Tsunami and N Kobayasht, Sohd
[ 7 ] M B Armand, Sohd State Iomcs 9/10 ( 1983 ) 745 State lomcs 11 (1983) 227
[8] M B Armand, lecture presented at VIth Intern Conf Sohd [ 19 ] J Przy~uskl, Z Flonaficzyk, K Such and W Wleczorek, m
State Iomcs, Garmlsch Partenktrchen, 1987 preparation
[9] Ch V Nichols, D J Wilson, C Booth and J R M Giles, m [20] A L e Mehaute, G Crepy, G MarceUm, T Hamalda and A
First Intern Symp Polymer Electrolytes, St Andrews, June Guyot, Polymer Bull 14 (1985) 233
1987 [ 21 ] A Revdlon and T Hamalda, Polymer Bull 6 (1982) 235
[ 10] P Passmleml, S Takkumakl, J Kankare and M Syrjama, [22] Y He, Z Chen, Z Zhang, C Wang and L Chen, Chem J
Sohd State Iomcs 28-30 (1988) 1001 Chinese Umv 2 (1986) 97
[ 11 ] E Linden and J R Owen, m First Intern Symp Polymer [23] W Wleczorek, K Such, H Wyo~hk, J P|ocharskl, Sohd
Electrolytes, St Andrews, June 1987 State Iomcs 36 (1989) 255, thts tssue
[24] W Wleczorek, K Such, S Gtowmkowskl, J Ptocharskl, to
12] E Linden and J R Owen, Sohd State Iomcs 28-30 (1988)
be pubhshed
994
[25] J E Weston and B C H Steele, Sohd State Iomcs 7 (1982)
13 ] J Przytuskl, Z Flormnczyk, W Krawlec, K Such and W
75
Wleczorek, m preparation
[26]J R Stevens and B E Mellander, Sohd State Iomcs 21
14 ] J Kelly, J R Owen and B C H Steele, J Electroanal Chem
(1986)
Interfacml Electrochem 168 (1984) 467 [27] S Skaarup, K West, B Zachau-Chnstlansen, Sohd State
15 ] J Kelly, J R Owen and B C H Steele, J Power Sources 14 lomcs 28-30 (1980) 975
(1985) 13 [28] J Ptocharskl and W Wleczorek, Sohd State Iomcs 28-30
16 ] M L Kaplan, E A Rletman, R J Cava, L K Holt and E A (1988) 979
Chandros, Sohd State lOnlCS25 (1987) 37
17 ] F M Gray, J R MacCallum and C A Vincent, Sohd State
Iomcs 18/19 (1986) 252