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Title: Blending Study of MgO-Based Separator Materials for Thermal Batteries

Abstract

The development and testing of a new technique for blending of electrolyte-binder (separator) mixes for use in thermal batteries is described. The original method of blending such materials at Sandia involved liquid Freon TF' as a medium. The ban on the use of halogenated solvents throughout much of the Department of Energy complex required the development of an alternative liquid medium as a replacement. The use of liquid nitrogen (LN) was explored and developed into a viable quality process. For comparison, a limited number of dry-blending tests were also conducted using a Turbula mixer. The characterization of pellets made from LN-blended separators involved deformation properties at 530 C and electrolyte-leakage behavior at 400 or 500 C, as well as performance in single-cells and five-cell batteries under several loads. Stack-relaxation tests were also conducted using 10-cell batteries. One objective of this work was to observe if correlations could be obtained between the mechanical properties of the separators and the performance in single cells and batteries. Separators made using three different electrolytes were examined in this study. These included the LiCl-KCl eutectic, the all-Li LiCl-LiBr-LiF electrolyte, and the low-melting LiBr-KBr-LiF eutectic. The electrochemical performance of separator pellets made with LN-blended materials wasmore » compared to that for those made with Freon T P and, in some cases, those that were dry blended. A satisfactory replacement MgO (Marinco 'OL', now manufactured by Morton) was qualified as a replacement for the standard Maglite 'S' MgO that has been used for years but is no longer commercially available. The separator compositions with the new MgO were optimized and included in the blending and electrochemical characterization tests.« less

Authors:
; ;
Publication Date:
Research Org.:
Sandia National Labs., Albuquerque, NM (US); Sandia National Labs., Livermore, CA (US)
Sponsoring Org.:
US Department of Energy (US)
OSTI Identifier:
800973
Report Number(s):
SAND2002-1458
TRN: US200224%%154
DOE Contract Number:
AC04-94AL85000
Resource Type:
Technical Report
Resource Relation:
Other Information: PBD: 1 Jun 2002
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; MAGNESIUM OXIDES; BATTERY SEPARATORS; ELECTROLYTES; MECHANICAL PROPERTIES; PERFORMANCE; PERFORMANCE TESTING; LITHIUM BROMIDES; LITHIUM CHLORIDES; LITHIUM FLUORIDES; THERMAL BATTERIES

Citation Formats

GUIDOTTI, RONALD A., REINHARDT, FREDERICK W., and ANDAZOLA, ARTHUR H. Blending Study of MgO-Based Separator Materials for Thermal Batteries. United States: N. p., 2002. Web. doi:10.2172/800973.
GUIDOTTI, RONALD A., REINHARDT, FREDERICK W., & ANDAZOLA, ARTHUR H. Blending Study of MgO-Based Separator Materials for Thermal Batteries. United States. doi:10.2172/800973.
GUIDOTTI, RONALD A., REINHARDT, FREDERICK W., and ANDAZOLA, ARTHUR H. Sat . "Blending Study of MgO-Based Separator Materials for Thermal Batteries". United States. doi:10.2172/800973. https://www.osti.gov/servlets/purl/800973.
@article{osti_800973,
title = {Blending Study of MgO-Based Separator Materials for Thermal Batteries},
author = {GUIDOTTI, RONALD A. and REINHARDT, FREDERICK W. and ANDAZOLA, ARTHUR H.},
abstractNote = {The development and testing of a new technique for blending of electrolyte-binder (separator) mixes for use in thermal batteries is described. The original method of blending such materials at Sandia involved liquid Freon TF' as a medium. The ban on the use of halogenated solvents throughout much of the Department of Energy complex required the development of an alternative liquid medium as a replacement. The use of liquid nitrogen (LN) was explored and developed into a viable quality process. For comparison, a limited number of dry-blending tests were also conducted using a Turbula mixer. The characterization of pellets made from LN-blended separators involved deformation properties at 530 C and electrolyte-leakage behavior at 400 or 500 C, as well as performance in single-cells and five-cell batteries under several loads. Stack-relaxation tests were also conducted using 10-cell batteries. One objective of this work was to observe if correlations could be obtained between the mechanical properties of the separators and the performance in single cells and batteries. Separators made using three different electrolytes were examined in this study. These included the LiCl-KCl eutectic, the all-Li LiCl-LiBr-LiF electrolyte, and the low-melting LiBr-KBr-LiF eutectic. The electrochemical performance of separator pellets made with LN-blended materials was compared to that for those made with Freon T P and, in some cases, those that were dry blended. A satisfactory replacement MgO (Marinco 'OL', now manufactured by Morton) was qualified as a replacement for the standard Maglite 'S' MgO that has been used for years but is no longer commercially available. The separator compositions with the new MgO were optimized and included in the blending and electrochemical characterization tests.},
doi = {10.2172/800973},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sat Jun 01 00:00:00 EDT 2002},
month = {Sat Jun 01 00:00:00 EDT 2002}
}

Technical Report:

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  • The deformation characteristics of pellets of electrolyte-binder (EB) mixes based on MgO were measured under simulated, thermal-battery conditions. Measurements (using a statistically designed experimental strategy) were made as a function of applied pressure, temperature, and percentage of theoretical density for four molten-salt electrolytes at two levels of MgO. The EB mixes are used as separators in Li-alloy thermal batteries. The electrolytes included LiCl-KCI eutectic, LiCl-LiBr-KBr eutectic, LiBr-KBr-LiF eutectic, and a LiCl-LiBr-LiF electrolyte with a minimum-melting composition. The melting points ranged from 313 C to 436 C. The experimental data were used to develop statistical models that approximate the deformation behaviormore » of pellets of the various EB mixes over the range of experimental conditions we examined. This report, discusses the importance of the deformation response surfaces to thermal-battery design.« less
  • We show that it is possible to manufacture strong macroporous ceramic films that can be backfilled with electrolyte to form rigid separator pellets suitable for use in thermal batteries. Several new ceramic manufacturing processes are developed to produce sintered magnesium oxide foams with connected porosities of over 80% by volume and with sufficient strength to withstand the battery manufacturing steps. The effects of processing parameters are quantified, and methods to imbibe electrolyte into the ceramic scaffold demonstrated. Preliminary single cell battery testing show that some of our first generation pellets exhibit longer voltage life with comparable resistance at the criticalmore » early times to that exhibited by a traditional pressed pellets. Although more development work is needed to optimize the processes to create these rigid separator pellets, the results indicate the potential of such ceramic separator pellets to be equal, if not superior to, current pressed pellets. Furthermore, they could be a replacement for critical material that is no longer available, as well as improving battery separator strength, decreasing production costs, and leading to shorter battery stacks for long-life batteries.« less
  • The Expanded Ocean Thermal-Structure (EOTS) analysis system, an application of the general-purpose Fields by Information Blending (FIB) methodology, is an advanced, comprehensive and flexible system for four-dimensional analysis of thermal structure from the ocean surface to the bottom. Using surface (ships, buoys, satellites) and sounding observations and information carried and accrued along the time axis from previous analyses and climatologies, analyses may be performed for any region and for any grid resolution in space and time. Significant variabilities in the vertical profile are represented by a set of thermal-structure parameters--absolute values, gradients and curvatures. Special provision is made for fine-resolutionmore » of thermal structure in the vicinity of the Primary Layer Depth and for restricting flow of information across land barriers. EOTS may be used for real-time synoptic analyses and, using available data bases, for production of historical sequences and climatologies. A wide variety of optional outputs includes horizontal and vertical sections of temperature and sound speed.« less
  • Ten commercial MgO powders were evaluated for their suitability to act as a binder in the separator of thermal batteries to immobilize the electrolyte when it is molten. One brand in particular, Maglite S from Calgon, outperformed all the others. This report describes the results of a characterization study of this MgO as well as similar materials from other commercial vendors. The study objective was to define the critical properties of Maglite S MgO that are responsible for its superior performance in thermal-battery separators. Separator mixes were prepared with the various MgO powders and the resulting powders and pellets weremore » characterized, to correlate key physical properties of these materials to select physical and chemical properties of the MgO powders used in their preparation. The MgO pore-size distribution was the only parameter that could be related to the deformation and electrolyte-leakage behavior of separator pellets. A potential replacement for the Maglite S is currently being qualified, since Maglite S MgO is no longer available.« less
  • This work was a preliminary investigation to determine if polyphenylquinoxaline (PPQ) or a codispersed mixture of polyvinylpyrrolidone (PVP) with PPQ could be used to replace cellophane as a separator in the zinc--silver oxide battery. The primary purpose was to compare its dimensional and chemical stability with cellophane and to determine if methods could be developed to lower its high inherent electrical resistance. Dimensional measurements were made in 45% KOH at 298 K (25 C) and 353 K (80 C). Chemical stability to oxidation was observed in KOH solution saturated with silver oxide at 353 K. In an effort to lowermore » the resistance of these thin film membranes, various methods were studied to develop porosity. Included among these were extraction of the PVP in boiling water, pyrolysis of the PVP, swelling of the films with phenol, and precipitation of the PPQ from acetone. Increasing the molecular weight of the PVP appears very promising, and additional studies are recommended since these polymers have good potential use as separators.« less