skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Ion conducting polymers as solid electrolytes. Final report, 1985-1986

Abstract

Electrically conducting polymers have recently been the subject of much interest. In particular, their potential as electrolytes in solid-state batteries has gained the attention of the U.S. Navy. Current ion-conducting polymers have conductivities too low by a factor of ten at operational temperatures. In order to be able to obtain suitable conductivities in these polymers, a thorough understanding of the mechanisms governing ion motion in them must be attained. The processes involved in the ion conduction of one particular polymer, poly(propylene oxide) or PPO, were studied in this research. Samples were prepared using an ion-implantation procedure developed as part of the project as well as by the traditional chemical complexing technique involving alkali-metal salt doping. The samples produced were analyzed using both differential scanning calorimetry and audio-frequency complex impedance measurements. Results indicate that the polarity of the salts has a major effect upon the activation volume and the glass transition of PPO. As a result of these effects, it seems that nonpolar anions may aid in increasing the cationic transport number of the polymer. More importantly, the first direct numerical evidence of a connection between the large-scale segmental motions of the polymer chains and the chains and the conductivity hasmore » been established.« less

Authors:
Publication Date:
Research Org.:
Naval Academy, Annapolis, MD
OSTI Identifier:
7253865
Alternate Identifier(s):
OSTI ID: 7253865
Report Number(s):
AD-A-171703/2/XAB; USNA-TSPR-139
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; ELECTRIC BATTERIES; SOLID ELECTROLYTES; IONIC CONDUCTIVITY; ANIONS; CATIONS; ION IMPLANTATION; LITHIUM; OXIDES; SALTS; SUBMARINES; THIOCYANATES; ALKALI METALS; ANTITHYROID DRUGS; CARBONIC ACID DERIVATIVES; CHALCOGENIDES; CHARGED PARTICLES; DRUGS; ELECTRIC CONDUCTIVITY; ELECTRICAL PROPERTIES; ELECTROCHEMICAL CELLS; ELECTROLYTES; ELEMENTS; HORMONE ANTAGONISTS; IONS; METALS; ORGANIC COMPOUNDS; ORGANIC SULFUR COMPOUNDS; OXYGEN COMPOUNDS; PHYSICAL PROPERTIES; SHIPS 250903* -- Energy Storage-- Batteries-- Materials, Components, & Auxiliaries

Citation Formats

Semancik, J.D.. Ion conducting polymers as solid electrolytes. Final report, 1985-1986. United States: N. p., 1986. Web.
Semancik, J.D.. Ion conducting polymers as solid electrolytes. Final report, 1985-1986. United States.
Semancik, J.D.. Wed . "Ion conducting polymers as solid electrolytes. Final report, 1985-1986". United States. doi:.
@article{osti_7253865,
title = {Ion conducting polymers as solid electrolytes. Final report, 1985-1986},
author = {Semancik, J.D.},
abstractNote = {Electrically conducting polymers have recently been the subject of much interest. In particular, their potential as electrolytes in solid-state batteries has gained the attention of the U.S. Navy. Current ion-conducting polymers have conductivities too low by a factor of ten at operational temperatures. In order to be able to obtain suitable conductivities in these polymers, a thorough understanding of the mechanisms governing ion motion in them must be attained. The processes involved in the ion conduction of one particular polymer, poly(propylene oxide) or PPO, were studied in this research. Samples were prepared using an ion-implantation procedure developed as part of the project as well as by the traditional chemical complexing technique involving alkali-metal salt doping. The samples produced were analyzed using both differential scanning calorimetry and audio-frequency complex impedance measurements. Results indicate that the polarity of the salts has a major effect upon the activation volume and the glass transition of PPO. As a result of these effects, it seems that nonpolar anions may aid in increasing the cationic transport number of the polymer. More importantly, the first direct numerical evidence of a connection between the large-scale segmental motions of the polymer chains and the chains and the conductivity has been established.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed May 28 00:00:00 EDT 1986},
month = {Wed May 28 00:00:00 EDT 1986}
}

Technical Report:
Other availability
Please see Document Availability for additional information on obtaining the full-text document. Library patrons may search WorldCat to identify libraries that may hold this item. Keep in mind that many technical reports are not cataloged in WorldCat.

Save / Share:
  • Objective is the study of protonic conduction in perovskite oxides, such as KTaO/sub 3/. Doped crystals of this material readily incorporates interstitial H/sup +/. The D/sup +/-H/sup +/ isotope effect was measured in Ni/sup 3 +/ and Co/sup 3 +/-doped KTaO/sub 3/. The defect structure of pure and doped KTaO/sub 3/ was studied using EPR, dielectric relaxation, and nonstoichiometry. Other studies underway include Sc/sub 2/O/sub 3/-doped ceria, dielectric relaxation in borate glasses, and preexponentials of conductivity in fast-ion conductors. (DLC)
  • A pulsed-field-gradient nuclear magnetic resonance spectrometer was successfully constructed, which is based on a superconducting magnet and has magic-angle spinning capabilities. A dewar facility is an integral part of this system so as to permit investigation of ionic diffusion down to 77 K, along with a sample heating arrangement for diffusion measurements up to 300 C. This spectrometer has been employed in the measurements of protonic diffusion coefficients in beta-alumina solid electrolytes and cation, anion, and self-diffusion coefficients and amorphous polymeric electrolytes.
  • This project has focused primarily on protons in perovskite-related oxides. Particular attention has been given to KTaO/sub 3/ containing acceptor (transition-metal ion) dopants, which is available as high quality single crystals, and for which the H/sup +/ concentration can be monitored through IR absorption. Techniques used for this study were: electrical conductivity, low-temperature dielectric relaxation, isotope effect on the conductivity (by substituting deuterons for protons), IR absorption and EPR Measurements on the dopants ions. We have observed several dielectric loss peaks, due to Ni, Co, and Mn dopants. No evidence for conduction by the oxygen-ion vacancy was found, but inmore » the reduced state it is possible to obtain electronic small-polaron hopping processes. Other work included the study of ceramic samples of Yb-doped SrCeO/sub 3/, for which a low activation energy for protonic migration of 0.65 eV was found. Finally, an approach to analyzing the pre-exponentials of conductivity was developed and applied in an extensive survey of different fast-ion conductors.« less
  • As an extension of prior work done in this laboratory on proton transport in NH/sub 4//sup +/-H/sub 3/O/sup +/..beta..''-alumina, we report here new proton diffusion coefficient and conductivity measurements on: (1) magnesia-stabilized NH/sub 4//sup +/-H/sub 3/O/sup +/ ..beta..''-alumina crystals with a substantially different stoichiometry than that reported earlier; and (2) NH/sub 4//sup +/-H/sub 3/O/sup +/ ..beta..''-gallate crystals where stabilization of the as-grown crystal involves sodium substitution in the spinel block. Proton diffusion coefficients of both compounds were measured over the temperature range 300 to 450K with the aid of a pulsed field gradient NMR technique, whereas a complex admittance methodmore » was used to obtain the protonic conductivities reported here for the same temperature interval. In the light of the present and earlier observations of protonic transport behavior, ideas were discussed concerning: (1) possible mechanisms of proton transport and (2) the role played by stoichiometry and the type of spinel-block stabilizing element in these ..beta..'' materials.« less
  • Results are presented on high temperature solid state cells employing 50:50 weight percent lithium germanium vanadium oxide-lithium iodide. The incorporation of lithium iodide in lithium germanium vanadium oxide resulted in higher pellet conductivities and improved the high rate performance of the solid state cells. The cells were comprised of a lithium-aluminum or lithium-silicon alloy as the anode and a CVD thin film of titanium disulfide as the cathode. The cells exhibited an open circuit potential of about 2.1 V at 300 deg C and could be discharged at current densities up to 0.5 ampere per square centimeter.