X-ray absorption studies of ZnCl{sub 2}-PEO and mixed salt ZnCl{sub 2}/KCl-PEO and ZnCl{sub 2}/CsCl-PEO complexes
- Brookhaven National Lab., Upton, NY (United States)
- Polytechnic Univ., Brooklyn, NY (United States)
ZnCl{sub 2}[polyethylene oxide (PEO)]{sub 12}, [0.33 ZnCl{sub 2} + 0.67 KCl](PEO){sub 12}, and [0.33 ZnCl{sub 2} + 0.67 CsCl](PEO){sub 12} complexes were studied by X-ray absorption in the temperature range of 25 to 120 C. The results for ZnCl{sub 2} (PEO){sub 12} show that the complex exists mostly as undissociated ZnCl{sub 2} with the Zn atom also coordinated with four O atoms from the PEO. The respective Zn-Cl and Zn-O bond distances are 2.2 and 2.05 {angstrom}. There is an increase in ion pairing with increasing temperature. The results for the mixed salt complexes are consistent with the formation of a mixture of ZnCl{sub 4}{sup 2{minus}} and ZnCl{sub 3}{sup {minus}} complexes with a Zn-Cl bond distance of {approximately} 2.26 {angstrom}. Complex formation differs in [0.33 ZnCl{sub 2} + 0.67 KCl](PEO){sub 12} and [0.33 ZnCl{sub 2} + 0.67 CsCl](PEO){sub 12}. This is attributed to the higher charge density of K{sup +}, which promotes ion pairing and shifts the ZnCl{sub 4}{sup 2{minus}}/ZnCl{sub 3}{sup {minus}} equilibrium.
- Research Organization:
- Brookhaven National Laboratory (BNL), Upton, NY
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 404665
- Journal Information:
- Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 10 Vol. 143; ISSN 0013-4651; ISSN JESOAN
- Country of Publication:
- United States
- Language:
- English
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