PMMA based gel electrolyte for EC smart windows S.A. Agnihotry a, *, Pradeep a , S.S. Sekhon b a National Physical Laboratory, Dr. K.S. Krishnan Road, New Delhi 110 012, India b G.N.D. University, Amritsar 143 005, India Received 9 September 1998; received in revised form 27 October 1998 Abstract Preliminary studies of gel electrolytes based on PMMA and solutions of the lithium salt LiN (CF 3 SO 2 ) 2 in propylene carbonate (PC) and the mixed solvent propylene carbonate+ethylene carbonate (PC+EC) are presented. The in¯uence of salt concentration on conductivity with dierent proportions of PMMA and dierent volume ratios of EC and PC has been investigated. Comparison of conductivity studies of the liquid electrolytes with the salts LiCF 3 SO 3 and LiN(CF 3 SO 2 ) 2 has also been made. The addition of PMMA to the liquid electrolytes increases the viscosity considerably without aecting their stable potential window resulting in thermally stable gels. The high conductivity attained by the gels (3 Â 10 À3 S cm À1 ) at room temperature and their moderate variation with temperature made them very promising for electrochromic window applications # 1999 Elsevier Science Ltd. All rights reserved. Keywords: Gel electrolyte; PMMA; LiN(CF 3 SO 2 ) 2 ; Smart windows; Mixed electrolytes 1. Introduction Electrochromic devices (ECDs) based on solid poly- meric electrolytes (SPEs) are desirable for development of energy ecient windows, so-called `Smart Windows'. A search has been going for elastomeric and adhesive electrolytes with high conductivity at room temperature and with electrochemical and ther- mal stability. In order to have an ecient and reprodu- cible performance of an ECD the ohmic drop across the device needs to be minimized. This can be achieved with an electrolyte having conductivity greater than 10 À4 S cm À1 at room temperature. Several approaches have been followed to prepare SPEs with such proper- ties. Conventional polymeric electrolytes such as PEO- Li (X) where PEO is polyethylene oxide and LiX is a Li salt, with large anions such as AsF 6 À , BF 4 À or CF 3 SO 3 À . Materials of such compositions can be iso- lated as mechanically strong, free standing ®lms but their conductivities are too low (10 À9 ±10 À5 S cm À1 at 258C) for use in ECDs. The conductivity of SPEs can be enhanced by using amorphous polymer hosts hav- ing a low glass transition temperature (Tg). However, it is generally observed that high conductivity is achieved at the expense of good dimensional stability. There have also been attempts [1] to increase the amor- phous domains of electrolytes containing crystalline polymers like PEO, by using a salt such as LiN(CF 3 SO 2 ) 2 . Such a salt with extensive dispersion of the negative charge on the anion has a plasticizing eect and easily forms complexes with PEO with excel- lent ionic conductivities in the range 5 Â 10 À5 S cm À1 . These electrolytes have some tendency to slowly crys- tallize. High conductivities, greater than 10 À4 S cm À1 at room temperature, can be attained by an alternative approach of gel electrolytes. In such polymer±salt±sol- Electrochimica Acta 44 (1999) 3121±3126 0013-4686/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved. PII: S0013-4686(99)00029-8 * Corresponding author.