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FOURTH QUARTERLY REPORT

I * I, 22 March 1966 to 21 June 1966

DEVELOPMENT O F HIGH ENERGY DENSITY PRIMARY BATTERIES

NASACR 72071

by

S. G. Abens, R. Corbett,, and W. C. Merz

prepared for

NATIONAL AERONAUTICS AND SPACE ADMINISTRATION

CONTRACT NAS 3-7632

Technical Management NASA Lewis Research Center

Cleveland, Ohio Space Power Systems Division

Mr. W i l l i a m A. Robertson

.

Livingston Electronic Corporation Montgome ryville, Pennsylvania

https://ntrs.nasa.gov/search.jsp?R=19660028395 2020-03-02T18:04:28+00:00Z

.

DEVELOPMENT OF HIGH ENERGY DENSITY PRIMARY BATTERIES

by

S.G. Abens, R. Corbett, and W . C . Merz

ABSTRACT

Studies of electrolytes and positive electrode construction for the development of p r imary CuF,-Li bat ter ies were conducted. P C electrolyte was not significantly affected by water contamination. Positive electrodes made from thermally decomposed CuF,. 2H,O gave better shelf life but showed inferior discharge character is t ics compared to electrodes made f rom normal CuF,. No beneficial effects f rom CoF3, SbF3, and MnF3 added to CuF, were observed. carbonate improved the wet shelf life of CuF,-Li cells.

Solubility of CuF, in NaC104-

Reducing the concentration of LiC104 in propylene

.

TABLE O F CONTENTS

Page No.

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1

ABSTRACT.. . . . . . . - . . . . . . . . . . . . . . . . . . . . . i

1. SUMMARY.. . . . . . . . . . . . . . * . . . . . . . . . * . . . . 1

2. INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3. DESCRIPTION O F EXPERIMENTAL WORK . . . . . . . . . . . . 4

3.1. ELECTROLYTE SYSTEMS STUDIES. . . . . . . . . . . . 4

3.1.1. Solubility of CuF, in NaC104-Propylene Carbonate Solutions . . . . . . . . . . . . . . . . . 4

Solubility of Electrolyte Salts in Propylene Carbonate and Methyl Acetate. . . . . . . . . - . . 6

3. 1. 2.

3.2. POSITIVE ELECTRODE STUDIES . . . . . . . . . . . . . . 8

3. 2.1. Evduat ion of Dried CuF, in Methyl Formate C e l l s . . . . . . . . . . . . . . . . . . . . . . . . . 8

Evaluation of Thermally Decomposed CuF,. 2H,O in Methyl Formate Cells . . . . . . . . . . . . . . 10

Evaluation of Conductors in Pasted CuF, Electrodes . . . . . . . . . . . . . . . . . . . . . . 12

3.2.2.

3.2. 3.

3.2.4. Evaluation of Thermally Decomposed CuF,. 2H,O in Propylene Carbonate Cells . . . . . . . . . . . . 15

3. 2. 5. Copper Fluoride Filter Mat Composition Study. . . 21

3.3. CELL SYSTEMS STUDIES. . . . . . . . . . . . . . 24

3. 3.1. Evaluation of CoF3, SbFs, and MnF3 as Additives to CuF, Electrode . . . . . . . . . . . . . . . . . . 24

Effect of LiClO, Concentration on Performance of Propylene Carbonate Cells . . . . . . . . . . . . . 31

Performance of CuF,-Li Cells at Various Dis- charge Rates . . . . . . . . . . . . . . . . . . . . . 36

3. 3. 2.

3. 3. 3.

4. APPENDIX. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

4.1. VARIANCE ANALYSIS O F CELL DISCHARGE DATA . . . . 41

LIST OF TABLES AND FIGURES

Page No.

TABLE I

TABLE I1

TABLE III

TABLE I V

TABLE V

TABLE VI

TABLE VI1

TABLE VIII

TABLE IX

TABLE X

TABLE XI

TABLE XI1

TABLE XIII

TABLE XIV

TABLE XV

Solubility of CuF, in NaC104-Propylene Carbonate Electrolyte. . . . . . . . . . . . . . . . . . . . . . - . . . 5

Specific Conductance of Salt Solutions in Methyl Acetate and Propylene Carbonate . . . . . . . . . . . . . . . . . . 7

Discharge Performance of Dried CuF, in ME-LiC104 Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

Performance of CuF,, 2H,O and Decomposition Products with Li anodes in LiClO,-MF Electrolyte. . . . . . . . . . 11

Conductive Material Evaluation . . . . . . . . . . . . . . . 1 3

Performance of Decomposed CuF,. 2H,O with Li Anodes in LiC104-PC Electrolyte . . . . . . . . . . . . . . . . . . 17

Open Circuit Potentials of Decomposed CuF,. 2H,O vs. Lithium in LiClO,-PC Electrolyte . . . . . . . . . . . . . 18

Effect of Additive Concentration on Performance of CuFz Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . 22

Discharge Performance of CuF,-Li Cells Containing Additives. . . . . . , . . . . . . . . . . . . . . . . . . . . 25

Open Circuit Potentials of CuF,- Li Cells Containing Additives. . . . . . . . . . . . . . . . . . . . . . - . . . . 26

Performance of CuF,-Li Cells with LiClO,-PC Electrolyte. . . . . . . . . . . . . . . . . . . . . . . . . . 3 3

Performance of CuF,-Li Cells a t Various Discharge Rates. . . . . . . . . . , . . . . . . . . . . . . . . . . . 37

Variance Analysis Calculations . . . . . . . . . . . .- . . . 43

Minimum Mean Square for Statistical Significance. . . . . 4%

Power of the F T e s t . . . . . . . . . . . . . . . . . . . . . 44

LIST O F TABLES AND FIGURES (Continued)

Page No.

FIGURE 1 Discharge Per formance of CuF2-Li C e l l s . . . . . . 14

FIGURE 2 Discharge Per formance of Cells with CuFZ- 2H20 Decomposition Products . . . . . . . . . . . . . . . 19

FIGURE 3 Open Circuit Potentials of Cells with CuF; 2H20 Decomposition Products . . . . . . . . . , . . . . . 20

Open Circuit Potentials of CuF2-Li Cells with CoF,, SbF,, and MnF, Additives. . . . . . . . . . . 27 to 28

FIGURES 4 to 5

FIGURE 6 Discharge Performance of CuF2-Li Cells with COF,, SbF,, and MnF, Additives. . . . . . . . . . . 29

FIGURE 7 Effect of COF,, SbF3, and MnF, on Discharge Per formance of CuF2-Li Cel l s . . . . . . . . . . . . 30

FIGURES 8 t o 9 Discharge Performance of CuF2-Li Cells . . . . . . 34 to 35

FIGURE 10 Discharge Per formance of CuF2-Li Cells at Various Discharge R a t e s . . . . . . . . . . . . . . . 38

1. SUMMARY

Work was performed toward development of high energy density CuF,-Li pr i - m a r y cells. presently employs propylene carbonate-LiC10, electrolyte. The second cell is intended for the 1 to 10 hour discharge ra te and employs methyl formate- lithium perchlorate electrolyte. following areas:

One type of cell is intended for 100-1000 hour discharge rate and

The experimental work was performed in the

Electrolyte Systems Studies. pylene carbonate was found to be insensitive to water contamination level. After 360 hours of contact, copper ion concentration in the electrolyte was 19 micro-mols /mil l i l i ter .

Solubility of CuF, in solutions of NaC10, in pro-

Solubilities of various salts in propylene carbonate and methyl acetate were studied. cm" in methyl acetate and 0.097 ohm-1 cm" in propylene carbonate.

The conductivity of 25g of KAsFe/lOO ml of solvent was 0.11 ohm"

Positive Electrode Studies. in MF-LiC10, electrolyte when CuF, water 'content was below 0 .5 percent. To obtain normal discharge potential ( 2 . 9 - 3 . OV) at 10 mA/cm2, about 1 . 5 percent water in the CuF, appears necessary-

Pasted CuF, electrodes could not be discharged

Electrodes prepared f rom thermally decomposed CuF,. 2H,O produced higher cell polarization and lower active material utilization than is obtained with normal CuF,, but shelf life was significantly improved. at 35"C, best cathodic efficiency was 36 percent compared to 40 percent with- out stand.

After 30 days of stand

Evaluation of filter m a t CuF, composition showed good reduction efficiencies (up to 78 percent) with CuF, contents as high as 91 percent. nation with electrolyte improved performance of these cells significantly-

Vacuum impreg-

Cell Systems Studies. The effect of adding CoF,, SbF,, and MnF, to CuF, on discharge capacity and wet shelf life of CuF,-Li cells was studied. Addition of SbF3 had a detrimental effect, while the other additives did not a l ter cell p e r f o rman c e si gnif i c an tl y .

2

Reduction of LiC10, concentration in P C from 20 to 10 grams/100 ml solvent improved wet shelf life of the CuF,-Li cells; discharge performance a t 0. 67 mA/cm2 was not affected.

The best performance from CuF,-Li cells discharged at the (projected) l o o - , 200-, 500-, and 1000-hour ra tes was obtained a t the ZOO-hour ra te (73 per - cent CuF, reduction efficiency). 1000-hour ra te (23 percent efficiency), while 100- and 500-hour ra tes gave s imilar resul ts (58 percent and 47 percent efficiency, respectively).

The poorest resul ts were obtained a t the

.

.

3

2. INTRODUCTION

The purpose of this program is the development of high energy density pr i - m a r y battery systems suitable for space flight applications. bat ter ies , differing i n energy density and discharge rate requirements, a r e being sought: at the 100-1000 hour discharge rate, and 2) bat ter ies capable of delivering 50 watt hours per pound at the 1 hour discharge rate . F o r both types of bat- t e r ies , the CuF,-Li couple is being considered. For the low-rate battery, a propylene carbonate-lithium perchlorate electrolyte system is of pr imary in- te res t , while for the high ra te system a methyl formate-lithium perchlorate electrolyte is being investigated. These systems emerged as the most pro- missing at the conclusion of two previous year ly contract periods (NAS 3-2775 and NAS 3-6004).

Two types of

1) bat ter ies capable of delivering 200 watt hours per pound

F o r the 100-1000 hour battery, the main problem continues to be the limited wet shelf life capability of the system. The electrochemical efficiency of the CuF, electrode and the weight ratio of active to inactive mater ia l s in the cell a l s o require fur ther improvements in order to increase the potential energy output of the CuF,-Li battery.

F o r the 1-10 hour battery, improvements i n discharge capability at the r e - latively high current densities a r e required in order to increase the energy density potential of this system. for this battery, since r e se rve activation may be employed.

Wet shelf life is not an immediate problem

The present report descr ibes activity and tes t resu l t s obtained during the fourth quarter of the contract period.

*

4

3 . DESCRIPTION OF EXPERIMENTAL WORK

3. 1 ELECTROLYTE SYSTEMS STUDIES

3 . 1. 1 . Solubility of CuF, in NaClO,-Propylene Carbonate Solutions

The solubility of CuF, in LiC104-PC solutions has been studied and reported ear l ie r ( see NASA CR-54992, pages 10-17). It was found that the solubility increases with both increasing water content of the system and increasing LiC10, concentration. place thru the double decomposition of LiC104 and CuF,, - i. e .

It was believed that the dissolution of CuF, takes

CuF, t ZLiClO,----) C U ( C ~ O ~ ) ~ t ZLiF,

and that the main driving force for the reaction is the low solubility of L i F i n the electrolyte solution.

In order to determine the role of the electrolyte salt , and, particularly, of the alkali metal ion on the solubility of CuF,, studies of CuF, solubility i n solutions of NaC10, i n propylene carbonate were performed. The procedure employed was similar to that used in ea r l i e r t e s t s with LiC10, electrolytes, and the concentration of NaC10, employed (24g NaC104/100 ml PC) was about equivalent on a molar basis to the 20g/100 ml previously used for LiClO,.

The e 'ectrolyte solution and CuF, were introduced under an argon atmosphere into serum bottles, and water was added with a mic ro syringe to produce water contamination levels in the range of 70-3000 ppm. then placed on a laboratory shaker, and copper analyses on small aliquots of solution withdrawn with a syringe were performed periodically.

The serum bottles were

Results of copper analyses on the solutions af ter 24, 192, and 360 hours of agitation a r e presented in Table I, page 5. Karl F ischer analyses were also obtained a t various t imes and a r e presented, although the f igures do not represent the t rue water contents of the solution because of the presence of copper ions.

In comparing the present CuF, solubility resu l t s with ea r l i e r data for LiC10,- P C solutions, no significant effect of water contamination on the solubility of CuF, could be observed fo r the NaC10, solutions, while in the LiC10, solutions this effect had been strongly pronounced.

ferent batches of CuF, were employed), the resu l t s obtained with NaC10, a r e encouraging. and will include both compatibility and cell performance tes t s .

Although the two solubility tes t s were , not run side-by-side, and may not be directly comparable in some respects (dif-

Further work with "non-lithium" electrolytes i s in progress ,

I

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5

TABLE I

SOLUBILITY O F CuF, I N NaC104- PROPYLENE CARBONATE ELECTROLYTE

Propylene Carbonate: Sodium Perchlorate: G. F. Smith, vacuum dried 18 hours at 110°C;

Cupric Fluoride: Ozark Mahoning, 0.57’0 H,O as CuF; 2H20, untreated Electrolyte: 9 .2g NaC104/40 ml P C

MC & B, Lithium dried and redistilled; H20 = 20 ppm

H,O <20 ppm

H,O Conc. Agitation H,O Conc. ++ (Calc. init . ) Tim e (KFA) Copper Conc. (as Cu )

pg /ml (hrs. ) pg/ml pmols /ml Solution Color

124 0 24 80

192 160 36 0 220

37 2 0 24 340

192 490 36 0 440

1112

3350

124

0 24 950

192 1110 36 0 9 20

0 24 2770

192 31 30 36 0 2740

0 24 80

192 160 36 0 169

10.9 7 . 8

18.7

15.6 10 .9 18.7

15.6 12.5 18.7

15.6 12 .5 18.7

Light grey, green tinge Light grey, green tinge Light grey, green tinge



Grey green Grey green Grey green

Clear, water white Clear, water white Clear, water white

6

3 . 1 . 2 : Solubility of Electrolyte Salts in Propylene Carbonate and Methyl Acetate

In order to further investigate the possibility of replacing lithium with another alkali metal ion in the electrolyte a s a means of reducing CuF, decomposition during wet shelf stand of the cells, solubility of several sal ts in propylene ca r - bonate and methyl acetate was tested. The la t ter solvent was chosen for the study because of the outstanding stability with respect to lithium obtained in recent tes ts .

Salts were selected for study both a s possible electrolytes and to indicate solubility trends in the two solvents. were measured and used as an indication of solubility for the difficultly soluble sal ts .

The specific conductances of the solutions

The specific conductances of salt solutions in the two solvents a r e l isted in Table 11, page 7 . taken a s a criterion of their solubility in the two solvents. obtained for the fluorides was a s expected, with L i F producing the lowest conductivity. A relatively high conductivity was recorded for KAsF, in propylene carbonate; this appears to be the only salt among those studied which may serve a s an electrolyte in both methyl acetate and propylene carbonate.

The specific conductance of the difficultly soluble salts was The solubility trend

The conductivity of KC10, in P C was somewhat higher than expected.

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TABLE 11

SPECIFIC CONDUCTANCE O F SALT SOLUTIONS IN METHYLACETATEANDPROPYLENE CARBONATE

Temperature: 27.0" C 25g salt added to 100 ml solvent (saturated solutions except as indicated)

Solute

LiF

NaF4

K F (anh. )4

LiBr

NaBr3

KBr

~ i , cro4 '

Liz Cr O4

K2Cr04'

KC~O,

KAlF64

KAs Fs4

KCrF64

K 2TiFs

K2ZrF64

Solvent

MA* P C

MA P C

MA P C

MA P C

MA P C

MA P C

MA* P C

MA* P C

MA* P C

MA* P C

MA P C

MA P C

MA P C

MA P C

MA P C

Conductivity

1 . 0 4 3.23 x lo-' 5.38 lo-?

4.47 lo-?

5.85 8.78 10-3

3.04 1 0 - ~

4.35 IO-? 2.13 1 0 - ~

5.00 IO-?

7 .68 1.33

1.89 5.73 x l o +

4.75 1.24 1 0 - ~

7.70 IO-? 2.62 10-4

10.7 9 .71

2.10 IO-? 3.33 x lo-"

5.38

3.41

8.06 x

3.40 x

2.81 x lo-'

9.70 x 10"

6.33 x

1.66 x lo-'

Compl

Rem a rks

01 tely dis d

Solution dark green (sat 'd)

Solution green

Solution green

Completely dissolved

:: Treated methyl acetate (lithium dried and distilled). Dried for 20 hours at 50 " C in vacuum oven. Dried for 20 hours at 100°C in vacuum oven. Dried for 60 hours at 100°C in vacuum oven. Used as received from manufacturer.

3

8

3 . 2 . POSITIVE ELECTRODE STUDIES

3 . 2. 1 . Evaluation of Dried CuF, in Methyl Formate Cells

A number of discharge tes ts had previously been performed with pasted CuF, electrodes a t current densities as high a s 15 mA/cm2 (see page 25, NASA CR-54920). being in the order of 0 . 8 to 1. OV at -15°C.

Initial cell polarization at this current density was not excessive,

A subsequent ser ies of pasted electrodes were constructed in order to evaluate the effect of various conducting mater ia ls on cell performance. to discharge these cells a t 10 mA/cm2, all cells , including those with the previously developed and tested electrodes, polarized severely. It was concluded that the entire unexpected behavior was caused by the use of a substantially dr ie r CuF, in making the pasted electrodes compared to the mater ia l used in previous tests. types of CuF, were performed, both as received from the manufacturer and after drying treatment a t Livingston Electronic Corporation.

In attempting

To further investigate this phenomenon, cell tes ts with several

Three-plate cells with pasted CuF, and sheet lithium electrodes were constructed as previously described. The CuF, electrodes were about 0 .040" thick and had a theoretical capacity of about 1 . 0 AH. The paste composition was 100 par t s CuF,, 10 par t s graphite, and 1 par t cellulose acetate, with 10 percent ethyl alcohol - 90 percent ethyl acetate as the pasting solution. glass fiber mat, 0 . 0 2 " thick, was used for electrode separation. Discharge tests were performed at 300 mA (10 mA/cm2) at -15°C in LiCIO,-methyl for mate electrolyte (50g salt/100 ml solvent), and the resul ts obtained with the various mater ia ls a r e shown in Table 111, page 9 .

A

Performance of the cells can be related directly to the amount of water con- tained by the CuF, used to prepare the electrodes. formed a s expected from previous tes ts when the water content was above one (1) percent. However, a f te r argon s t ream drying to a water content below 0 . 3 percent, cell polarization was sufficiently severe to reverse polarity of the cells upon closing of the discharge circuit. Material f rom Lot 9, which had a water content of about 0 . 4 percent a s received from the manufacturer, gave equally poor resul ts .

Material f rom Lot 7 per -

The above results appear to indicate that completely dehydrated CuF, is too 'insoluble in the LiClO,-MF electrolyte to allow discharge a t 10 mA/cm2. A water content of one (1) percent seems to be required for discharge at the 1- 10 hour ra te . appear to be prohibitively high.

Fo r a reserve-activated system, this water content does not

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3 . 2. 2. Evaluation of Thermally Decomposed CuF,. 2H,O in Methyl Formate Cells

The thermal decomposition products of CuF,. 2H,O were identified in ear l ie r X-ray studies (see NASA CR-54992, pages 20 to 22), and were f,pund to con- s i s t mainly of hydroxy fluorides CuOHF and CuOHF- CUI?, as well as an un- identified compound with a major peak intensity a t 4. 15 A . These mater ia ls appeared to be relatively insoluble in the LiC10, electrolyte solutions, and have an equivalent weight which is slightly lower than that of normal CuF,. Thus, the CuF,. 2H,O decomposition products were of interest as possible cathodic reactants, and the discharge performance of thin pasted electrodes made with CuF,. 2H,O and i t s decomposition products was studied in positive- limited cells with lithium anodes and LiClO,-methyl formate electrolyte.

Materials used for the preparation of pasted electrodes included untreated CuF,. 2H,O, a mixture of 95 percent CuF, ( 0 . 5 percent H,O) and 5 percent CuF,. 2H,O, and thermal decomposition products of CuF,. 2H,O.

The pasted positive electrodes, and 3-plate tes t cells were prepared as described in Section 3 . 2. l . cm2 and -15°C; resul ts of the discharge tes ts a r e tabulated in Table IV, page 11.

Discharge tests were performed as usual a t 10 mA/

The CuF, - CuF,. 2H,O mixture produced electrodes having about the same discharge characterist ics as have been observed with electrodes made from CuF, a s received from the manufacturer and having an equivalent total water content (ca . 2 percent). Electrodes made from 100 percent CuF,. 2H,O gave s imilar discharge potential and electrochemical efficiency as the CuF, - CuF,. 2H,O mixture. 2H,O decomposition products could not be discharged a t 10 mA/cm2 (almost immediate polarity reversa l occurred at this cur ren t density).

However, cells built f rom electrodes containing the CuF,.

The above results further demonstrate that (1) water in the range of 1-2 per - cent may be necessary for rapid discharge of CuF,, and ( 2 ) the source of water is of no importance-it may be present a s an impurity in the original CuF,, o r i t may be added in the fo rm of CuF,. 2H,O.

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12

3. 2 . 3 . Evaluation of Conductors in Pasted CuF, Electrodes

To evolve CuF2 electrodes for high energy density, relatively high discharge ra te cells, the ratio of active to inactive mater ia l in the electrodes mus t be high.

In electrodes operating a t relatively high current densities, this may not be achieved a t the expense of conductivity of the mat r ix . lend good conductance, when added in small concentrations, a r e desired fo r such electrodes.

Thus, additives which

Three conductive mater ia ls were compared in cell t es t s with Dixon air spun graphite, which has been used in most cell tes ts to date. The conductors evaluated were Conductex SC and SA-40-220 (Columbian Carbon Company) and alkaline battery type nickel flake (Electric Storage Battery Company). Conductex SC i s a carbon black used for producing conductive film while SA- 40-220 i s being developed for battery applications.

Pasted CuF, electrodes were prepared a s described in the previous sections. The mix composition was 20 grams CuF, (Lot 7, H,O content ca. 1 . 5 percent), 1 gram conductive m?.terial, and 0 . 2 g ram cellulose acetate. After blending the dry components in a micronizer blender, pastes were prepared using a 10 percent alcohol - 90 percent ethyl acetate pasting solvent, and pasted onto expanded metal . After vacuum drying of the electrodes, three-plate cells with two lithium electrodes and glass fiber separation were assembled, activated with LiClO,/MF electrolyte (50g salt/100 ml solvent), and discharged a t 10 mA/ cm2 at -15°C. in Table V, page 13, and voltage-time data for the best of the three cells in each group a r e plotted in Figure 1, page 14.

Construction data and discharge resul ts for the cells a r e l isted

In this test ser ies , the cells which had carbon black in the CuF, paste mix gave better discharge performance than those with either graphite o r nickel flake at the same concentration. Cell performance replication was comparatively poor, except for cells which had nickel flake additive. of cells having graphite conductor has not been characterist ic to this paste composition in ear l ier tests (see NASA CR-54920, pages 22 and 23). However, the performance of the best cells with carbon black additive was quite encouraging, with CuF, reduction efficiencies as high a s 65 percent a t the ca. 2 hour discharge rate. Since the active mater ia l i n these electrodes is in the order of 80-90 percent including the weight of the si lver grid, high energy densities should be possible in this construction even at the relatively short discharge t imes .

Also, the poor performance

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3 .2 .4 . Evaluation of Thermally Decomposed CuF,. 2H,O in Propylene Carbonate Cells

Drying of CuF, by various methods has been investigated previously in attempting to improve the shelf life of activated CuF2-Li cells. water is known to exist as CuF2-2H,0, thermal decomposition of this compound was also studied. mal decomposition products in the LiClO,-propylene carbonate electrolyte were obtained, cell tests with decomposed CuF,. 2H,O electrodes were ini- tiated.

Since the

After some indications of low solubility of the ther-

The positive active mater ia l was prepared by heating CuF,. 2H,O in a tube swept by argon for 57 hours at 180-188°C. The resulting material showed a 23 percent weight loss f rom the dihydrate, and the composition was shown by X-ray analysis to be

Unknown Material* 63'70 CuOHF 28% CUOHF. CUF, 1270

TOTAL 10370

*Major peak intensity at 4.15 A. 0

Fil ter mat electrodes were prepared by the methods described in previous re- ports ( see NASA CR-54803, pages 67-72). The mix composition was

Active Material 104 Graphite 14 Paper Fiber 7.

Twelve 3-plate CuF,-Li tes t cells were constructed and activated with 15g LiClO,/lOO ml propylene carbonate electrolyte (water 50 ppm by K a r l Fischer analysis). protruding) in polyethylene containers measuring 4 x 4 x 3 inches. Four cells were put on discharge thru 200-ohm loads at 35"C, while the remaining cells were discharged under the same conditions after open circuit stand periods of 9 and 30 days a t 35°C.

Groups of four cells were assembled and sealed (with cell terminals

Discharge data for the cells a r e summarized in Table VI, page 17, and cell open circuit potentials during stand are given in Table VIL page 18. time data during discharge and open circuit stand have been plotted for the last cell in each group in Figures 2 and 3, pages 19 and 20.

Voltage-

16

In comparison to the normal CuF,, the decomposed CuF2. 2H,O produced higher cell polarization at the ZOO-ohm loads. All cells , except Cell # 1 , fell in potential to below 2 . 5V after 4 hours of discharge. green electrolyte color in Cell #1, i t was suspected that this cell had been con- taminated with water, possibly thru the use of an improperly dried hypodermic syringe. duced to about one-half of that obtainable f rom normal CuF,. potential during stand, and capacity after stand were significantly better, however . higher than for cells which had no stand, with only a slight reduction in active mater ia l utilization.

Because of the distinctly

The positive active mater ia l utilization efficiency was likewise r e - Open circuit

The average discharge potential of cells after 30 days of stand was

The decomposed CuF,. ZH20 appears to be reducible in the LiClO,-propylene carbonate electrolyte, but i t s low solubility does not permit the normal 200- ohm discharge. can likewise be explained in t e rms of i t s lower solubility in the electrolyte solution. Further studies on this mater ia l a r e required to fully evaluate i t s properties and possible advantages over normal CuF, a s the active mater ia l of the cell .

The significantly better shelf life observed with this mater ia l

17

I I I'

0 "I

I I I

0 0 0 0 m m m m 0 0 0 0 m m m m

8

9

z q a

m a + N d a

m m > N d d

2 q a

2 q a

rn

. z l $ a

m N m m m m m m m m m m . . . .

r - m r - N m m m m m m m m . . . .

O N O N m m * m m m m m . . . .

0 0 0 0 m m m m m m m m . . . .

0

9 % a

u1

18

I-

i

4

19

-

20

. -

. I . I .

.

. , . . .

k

t

21

3 . 2. 5. Copper Fluoride Fi l ter Mat Composition Study

Fur ther composition evaluation was performed for the CuF, filter mat electrodes during the pas t quarter . CuF, contents than the 82. 5 percent commonly used may be satisfactory, but discharge results showed a la rge degree of variation between replicate cells. It appeared that poor wetting of the cathode ma t r ix with the electrolyte solution may be causing the non-uniformity in cell performance. m o r e evident in cel ls in which a high ratio of graphite to paper fiber was used.

Previous tests had indicated that subs:antially higher

This condition was

In the present test series, four tes t cells for each positive electrode composition were constructed and tested. The filter ma t electrodes were prepared as descr ibed previously, and the graphite and paper pulp concentrations were varied over the range of 4-16 and 2-8 grams/lOOg CuF,, respectively. The t e s t cel ls had the usual sandwich construction with one f i l ter m a t CuF, electrode, and two lithium slab electrodes separated by 0 . 0 3 in. microporous rubber. After addition of 15g LiC104/100 ml P C electrolyte, two cells in each group were placed i n a desiccator and maintained under vacuum until no further gassing f rom the electrodes and separa tors could be observed. The vacuum was then released, and the electrolyte levels in the cells were adjusted to the previous height. The remaining two cel ls in each group were filled by the normal procedure. temperature of 35°C. cells is given in Table VIII, page 22 (electrolyte volume for cel ls 1-1 thru 3 - 4 was not obtained because leaks in the polyethylene envelopes caused an un- determined amount of loss during filling. ).

Discharges were then started at a constant current of 21 m A and a A summary of construction and discharge data for the

Vacuum impregnation improved cell performance significant1 y for the higher CuF, content mixes (Cells 1 - 1 thru 2-4). F o r the cells having the higher additive levels, no apparent benefit from vacuum impregnation resulted.

Considerable variation in CuF, reduction efficiency among replicate cells was again encountered over the ent i re composition range. were obtained with cel ls having the highest graphite content (16g/lOOg CuF,). However, increasing the paper fiber content appeared to affect the performance adversely, which may be an indication that this mater ia l (S & S fi l ter paper pulp, acid washed) causes some contamination in the cell. to replace some of the f i l ter paper pulp with other, preferrably conductive, fibrous mater ia l (such as graphite f ibers) .

The highest efficiencies

It may be possible

A variance analysis of the cell performance data is presented in Appendix I.

22

I I 4 m I Fr-

0 0 I l m m 1 1 . . I I "

. I . . . . . . 4 l 4 N N 4 m N

c o 4 F O o o m o m m N m . . . .

It * I I I I I I I I I l l 1

* * I I I I 1 1 1 1 I l l 1

4 4 4 4 m m m m

m m m m c o c o c o c o

""

* * * *

" N N ON"

c o c o c o c o 9999 4 4 4 4

* e * * c o c o c o c o

23

m o\

N

0

* N

00

4 4 6 0

N m . .

6

2

Ln

9

m N d

m 9

* * * * 0009 o o m o 9 9 F 9 b b 9 b . . . . . . . .

k

00000000 00000000

r -6 0 c o o 1 m N m I N

. . I *

m 9 9 m 0 0 o m d c - v

* * m m o m r - r - F 9 . . . .

4 4 4 4 00000000

0 0 0 0 0 0 0 0

9-99 4 4 4 4

m 2 0 c N 4 - m k .d ccc k 0 tH

9 In

N

3 0 e, P e, M cd

0 > a ld

4

c, d

2

24

3 .3 . CELL SYSTEMS STUDIES

3. 3 .1 . Evaluation of C O F ~ , SbF3, and MnF3 as Additives to CuF, Electrode

Evaluation of additives to f i l ter ma t CuF, electrodes was undertaken in o rde r to study methods for improving shelf l i f k of CuF,-Li cells having propylene carbonate electrolyte. Since it has been demonstrated that presence of water is detrimental to shelf life of the cells, mater ia ls which a r e known to reac t with water were selected for addition to CuF, during preparation of the electrodes. It was hoped that these additives would decompose the contamination water r e - leased by CuF, during stand, thus reducing its solubility in the electrolyte solution and improving capacity retention of the cells.

The additives selected for testing were COF, and MnF3 a t a concentration of 4 grams/100 grams of CuF2, and SbF, a t 6 grams/lOOg CuF, (the concentration of additive being roughly proportional to its molecular weight). were added to CuF, pr ior to jar milling with graphite under heptane. ma t composition for construction of the electrodes was 100 par ts CuF,, 14 par t s graphite, and 7 par ts paper fiber, plus additive. Electrodes were prepared as described previously by pressing 1. 5 x 1. 5 in; sections of the f i l ter mat onto expanded silver and removing the residual heptane by vacuum drying. Three electrode cells with outside lithium electrodes and MPR separation were constructed and tested for performance with LiClO,-PC electrolyte (15 g rams sal t / 100 ml solvent).

These The f i l ter

Six cells for each type of additive, and six having no additive were constructed and tested. TWO cells f rom each group were discharged thru 200-ohm at 35°C after one (1) day open circuit stand a t 35°C; the remaining cells were discharged after stand periods of 8 and 14 days a t 35°C.

Construction and discharge data for the cells a r e summarized in Table IX, page 25, while the open circuit potentials of cells during stand a r e listed in Table X, page 26. Figures 4 to 7 , pages 27 to 30.

Voltage-time data for the best cell i n each group a r e presented in

Addition of SbF3 had a clearly detrimental effect on both discharge capacity and capacity retention after stand. significant effect on the character is t ics of the cells. average capacity loss of about 50 percent af ter 8 days stand a t 35°C. days at the same temperature, only half of the cells had retained any capacity above a load potential of 2 . 5 volts. Inspection of the cells after discharge indicated that dissolution of the CuF, had taken place, which still appears to be the main cause of capacity decay during stand.

Addition of CoF3 and MnF3 appeared to have no

After 14 These cells suffered an

25

m M > E-l Q n 4

H

H

U z W

3 ; 2 0 u

dl u w u z

p: 0 6(

2

m 4 I a m I . . I N N

4

co N

9 I r - I . I N

m I b I . I N

w PI w * d 4 z u Cn H n

a, S i

h

3 u E: 0 a 0) m ld

* Q

I 26

m l

c, 0

O m m m N N C O c o 1 1 1 1 1 1 1 1 m g L n m 0 m d N 1 1 1 1 1 1 1 1 . . . . . . . . 1 1 1 1 1 1 1 1

I I I I I I I I * 1 1 1 1 1 1 1 1 I I I I I I I I m 4 N m N N m m . 4 7

r - c O c o N c c ) c O C O r - 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 N 0 4 ( 3 \ 0 ( 3 \ 0 d 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 . . . . . . . . "4 L I I 1 1 1 1 1 1 1 1 1 1 1 1 1 l m m m N m N m m

m .

* m m 4 N d 4 r - 1 1 1 1 1 1 1 1 m 0 ( 3 \ m m 4 N N 1 1 1 1 1 I I I . . . . . . . . 1 1 1 1 1 1 1 1 m m N m N m m m

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 q

N 1 1 1 1 1 1 1 1 4

9 4 0 9 C O + * r - 1 1 1 1 1 1 1 1 r n O d M * d d N

4 I I I I I I I I 1 1 1 1 1 1 1 1 m m m m N m m m ~ 1 1 1 1 1 1 1 1 I I I I I I I I 1 1 1 1 1 1 1 1 . . . . . . . .

27

. . - . . - ._ . . . , . . : . .

. .

30

. ... .

31

3 . 3. 2 . Effect of LiCLO, Concentration on Performance of Propylene Carbonate Cells

The effect of solute concentration on the solubility of CuF, in propylene car - bonate-lithium perchlorate electrolytes has been studied previously (see NASA CR-54992, pages 10 to 14); in these tests, increasing the concentration of LiC104 caused higher solubility of CuF, in the electrolyte. cell performance tes ts were conducted i n order to establish a correlation between the resul ts of the compatibility studies and cell performance, and to determine the optimum electrolyte concentration for the 100-1 000 hour discharge rate CuF,- Li cells.

During the past quarter ,

The positive electrodes were prepared by the standard fi l ter m a t technique and had the composition

CuF, 100

Paper Fiber 7 . Graphite 14

Three-plate test cel ls with two lithium negative electrodes and 0.03 in. microporous rubber separation were constructed and assembled in groups of three cells in hermetically sealed j a r s .

Electrolyte solutions were prepared with lithium-dried and fi l tered propylene carbonate, and lithium perchlorate dried in vacuum a t 110°C for 16 hours. The concentrations employed in this tes t were IO, 20, 30, and 40 g r a m s of LiC10, per 100 mil l i l i ters of propylene carbonate.

Construction and discharge data for the cells with 10 and 20 grams LiC10, per 100 ml P C are summarized in Table XI, page 33. Cells having the higher electrolyte concentrations showed very poor initial discharge performance ( less than 12 hours to 2 . 5 V F at 20 mA and 35°C) and were discontinued f rom the test .

With no open circuit stand, capacity at the 20 m A (ca. 0 . 7 mA/cm2) discharge ra te a t 35°C was about equal for both groups of cells. However, after 10 days of activated stand a t O"C, the CuF, reduction efficiency was 71, 73, and 77 percent for the three cells having the l O g / l O O ml electrolyte, and 54, 60, and 6 2 percent for the cells having the 20g/100 ml solution. After 24 days of acti-

. vated stand a t O"C, two of three cells with the lower electrolyte concentration retained capacity above 2 .5 V F (58 and 19 percent reduction efficiency), while all three cells with the m o r e concentrated electrolyte failed to give any capacity a t this point. and after open circuit stand a r e presented in Figures 8 and 9, pages 34 and 35.

The discharge data for the best of three cells in each group before

3 2.

The results of this tes t indicate an improvement in wet shelf life with lower LiC10, concentration; this may be explained in t e r m s of the lower solubility of CuF, i n the less concentrated solution. Further cell tes ts with a range of more dilute electrolytes will be performed in order to identify the concentration which gives the best discharge and shelf life character is t ics .

33

* o I C - c o I I I I . . I I I I N N 1 I I

W X w J

b 9

Y

I I I

0 0 0 0 0 0 4 4 d d d d

36

3. 3 . 3. Performance of CuF,-Li Cells a t Various Discharge Rates

In order to fur ther character ize the performance capabilities of the "low-rate" CuF,-Li system, discharge performance of cel ls having the usual f i l ter-mat electrode construction (14 g r a m s of graphite and 7 g r a m s of paper fiber per 100 g rams of CuF,) was determined at various discharge loads. lyte was 15g LiC104/100 ml of propylene carbonate, and microporous rubber separation and s lab lithium electrodes were employed as before. met r ic electrode area of the three-plate (1 CuFz electrode, 2 Li e lectrodes) cells was 29 cmL. 100, 200, 500, and 1000 ohms. The construction and discharge data a r e summarized in Table XII, page 37, and voltage-time curves for the best cell a t each discharge r a t e a re presented i n Figure 10 , page 38.

The electro-

The geo-

Discharges were conducted a t 35°C thru resis t ive loads of

In t e rms of CuF, reduction efficiency, the best performance was obtained f rom cells discharged thru 200 ohm loads (ca. 250 hour discharge); the highest reduction efficiency in this group (best of three cel ls) was 7 3 percent a t an average discharge potential of 3 . 04V to a cut-off voltage of 2. 5V. With 100 ohm loads ( ca . 100 hour discharge) , the best efficiency was 58 percent a t 2.90V average discharge potential. With lower discharge ra tes , the performance again decreased, the best-of-three-cells f igures being 47 percent efficiency a t 3.20V average thru 500 ohm load (ca . 400 hour discharge), and 2 3 percent efficiency at 3.14V average thru 1000 ohm load (ea . 400 hour discharge) .

Inspection of discharged cel ls showed copper-colored deposits on the lithium, particularly i n the cel ls which were discharged thru 1000 ohm. Dissolution of CuF, was again evident in this tes t s e r i e s , and probably contributed to the decreased performance of the cells with increasing discharge t ime. A means fo r minimizing the effect of dissolved copper mus t be developed before the present system can be utilized a t either the longer discharge t imes, o r where wet shelf life is required.

,

i I

i

I

I 1 ~

I I I

1

37

TABLE X U

PERFORMANCE O F CuF,-Li CELLS AT VARIOUS DISCHARGE RATES

(LEG Test No. 640-16)

Cell Theo. CuF, Time to Average Disc. Capacity to Efficiency No. Capacity, AH Load, 0 2. 5 VF , h r s . Potentials, Volts 2. 5VF, AH 70 -

1 5.67 500 432 3. 14 2.68 47

2 5 .92 500 36 0 3.07 2.21 37

3 5 .52 500 408 3.20 2 .62 47

4 6. 1 3 1000 192

5 5 .98 1000 36 0

6 5 .95 1000 432

7 5 .89 200 172

8 5 . 3 3 200 258

9 5 .42 200 247

10 5 .42 100 108

11 5.24 100 79

12 6 .15 100 17

3.11 0.60 10

3.18 1 .14 19

3. 14 1 .35 23

2. 89 2.49 42

3.04 3.90 73

3.04 3.72 69

2.90 3 .14 58

2 .79 2.20 42

39

4. APPENDIX

41

4. APPENDIX

4.1. Variance Analysis of Cell Discharge Data

The analysis of variance technique w a s applied to the data of Section 3 . 2. 5

The t e s t was designed with three factors to be studied, graphite and paper concentrations and the effect of vacuum impregnation of the electrolyte into the cell .

To 50 g r a m s of CuF,, graphite was added in amounts of 4, 8, and 16 grams, and paper in amounts of 2, 4, and 8 grams. Four cells were fabricated, two being activated by standard procedure and two using vacuum impregnation.

In the variance analysis, the four cells with equal graphite and paper concentrations w e r e grouped together so that the factor of vacuum impregnation is not included in the analysis.

The m e a s u r e of cell performance was taken to be the percent utilization of CuF, in the cathode.

The m e a s u r e of the variance due to e r r o r was taken to be the sum of the squares within each cell.

Table XIII, page 43, shows the resul ts of the variance analysis calculations up to the evaluation of the F ratio.

The final resu l t s of the variance analysis a r e given in Tables XIV and XV, page 44.

Table XIV lists the minimum mean square f o r a given level of significance of the respective mean square. particular sample and the e r r o r mean square. F t e s t f o r those values of F listed in Table XIII. percentage likelihood of rejecting the hypothesis that the particular groups have the same mean i. e . the same average cell efficiencies.

These were calculated using the F rat io of the Table XV l i s t s the power of the

This figure represents the

-

42

I Since the mean square variation f o r both paper and graphite concentration (420 and 474) is l e s s than the minimum mean square for significance a t the 5 percent level (623) , this would imply that neither paper concentration nor graphite concentration, a s independent factors a r e directly related to cathode efficiency.

On the other hand, since the variance t e r m due to graphite-paper interaction (1222) exceeds the mean square variation for the one (1) percent significance level the implication is that cell performance is m o r e dependent upon the ratio of graphite to paper than on the concentration of either one of the components.

The data discussed above show that there is significant difference in cell efficiencies when the cathode composition is varie'd.

43

Source of Variation

Between paper P d P groups

TABLE XLII

VARIANCE ANALYSIS CALCULATIONS

Degrees of sum of Freedom Squares

2 Between graphite groups

2 840

4 Graphite /paper interaction

E r r o r

TOTAL

27

35

Mean I I F I I

Square Ratio

420 2.26

948 47 4 2.54

4888 1222 6.58

5008 186

11684

44

TABLE XIV

M I N M U M MEAN SQUARE FOR STATISTICAL SIGNIFICANCE

Signifi c anc e L eve1

Graphite Variation

Paper Variation

Graphi te /Paper Interaction

5 %

6 2 3

6 2 3

508

- 170

1021

1021

7 6 5

-

TABLE XV

POWER O F THE F TEST

1% 5 % - Graphite Variation 6 5 38

Paper Variation 58 32

Graphi te /Paper Interaction 97 8 8

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North American Aviation, Inc. 12214 Lakewood Boulevard Downey, California 90241 Attn: Burden M. Otzinger

Dr. JohnOwen P. 0. Box 87 Bloomfield, New J e r s e y 07003

Power Information Center University of Pennsylvania Moore School Building 200 South 33d St ree t Philadelphia, Pennsylvania 19 1 04

Philco Corporation Division of the Ford Motor Co. Blue Bell, Pennsylvania 19422 Attn: Dr. Phill ip Cholet

Radiation Applications, Inc. 36-40 37th Street Long Island City, New York 11101

Radio Corporation of America Ast ro Division Hightstown, New J e r s e y 08520 Attn: Seymour W i n k l e r

7

Radio Corporation of America P. 0. Box 800

Attn: I. Schulman I Princeton, New J e r s e y 08540

Sonotone Corporation Saw Mill River Road Elmsford, New York 10523

!

, Attn: A. Mundel I I

Texas Instruments, Inc. 13500 North Central Expressway Dallas, Texas 75222 Attn: Dr. Isaac Trachtenberg

Thomas A. Edison Research Lab. McGraw Edison Company Watchung Avenue West Orange, New J e r s e y 07052 Attn: Dr. P. F. Grieger

TRW, Inc. TRW Systems Group One Space P a r k Redondo Beach, California 90278 Attn: Dr. A. Krausz, Bldg. 60,

R. Sparks Room 929

TRW, Inc. 23555 Euclid Avenue Cleveland, Ohio 44 11 7 Attn: Librar ian

Tyco Laborator ies , Inc. Bear Hill, Hickory Drive Waltham, Massachusetts 02154 Attn: W. W. Burnett

I Union Carbide Corporation Development Laboratory Library P.O. Box 6056 Cleveland, Ohio 44101

Union Carbide Corporation P a r m a Research Lab. P. 0. Box6116 Cleveland, Ohio 44 1 0 1 Attn: L ib ra ry

University of California Space Science Laboratory Berkeley, California 94720 Attn: Dr. C. W. Tobias

University of Pennsylvania Electrochemistry Laboratory Philadelphia, Pennsylvania 191 04 Attn: Prof. J. O'M Bockris

Western Elec t r ic Company Suite 802, RCA Building Washington, D. C. 20006 Attn: R. T. Fiske

Westinghouse Electric Corp. Research & Development Center Churchill Borough Pittsburgh, Pennsylvania 15235 Attn: Dr. A. Langer

Whittaker Corporation 3850 Olive Street Denver, Colorado 8 0237 Attn: Borch Wendir

W h i t t a k e r Corporation P. 0. Box 337 Newbury Park , California 91320 Attn: John Rhyne

Whittaker Controls & Guidance 9601 Canoga Avenue Chatsworth, California 9131 1 Attn: Dr. M. Shaw

I

8

Yardney Electr ic Corporation 40-50 Leonard Street New York, New York 10013 Attn: Dr. George Dalin

Bell Laboratories Murray Hill, New J e r s e y 07971 Attn: U. B. Thomas

The Boeing Company P. 0. Box 3707 Seattle, Washington 98 124

Borden Chemical Company Central Research Lab. P. 0. Box 9524 Philadelphia, Pennsylvania 9

Burgess Battery Company Foot of Exchange Street Freeport , Illinois 6 1032 Attn: D r . Howard J. S t rauss

24

C & D Batteries Division of Electr ic Autolite Co. Conshohocken, Pennsylvania 19428 Attn: D r . Eugene Willihnganz

Calvin College Grand Rapids, Michigan 49506 Attn: Prof. T. P. Dirkse

Catalyst Research Corporation 6101 Falls Road Baltimore, Maryland 21209 Attn: J. P. Wooley

Chem-Cell Inc. 150 Dey Road Wayne, New J e r s e y 07470 Attn: P. D. Richman

Delco Remy Division General Motors Corporation 2401 Columbus Avenue Anderson, Indiana 46 0 1 1 Attn: Dr. J. J. Lander

Douglas Aircraf t Company, Inc. A stropowe r Lab0 ra tory 2121 Campus Drive Newport Beach, California 92663 Attn: Dr. Ca r l Berger

Dynatech Corporation 17 Tudor S t ree t Cambridge, Massachuset ts 02138 Attn: R. L. Wentworth

Eagle -Picher Company Pos t Office Box 47 Joplin, Mis souri 648 02 Attn: E. M. Morse

Elgin National Watch Company 107 National Street Elgin, Illinois 60120 Attn: T. Boswell

E lec t r ic Storage Bat tery Company Missi le Bat tery Division 2510 Louisburg Road Raleigh, North Carolina 276 04 Attn: A. Chreitzberg

Elec t r ic Storage Bat tery Company C a r l F. Norberg Research Center 19 W e s t College Avenue Yardley, Pennsylvania 19068 Attn: Dr. R. A. Schaefer

Elect roc himi ca Corporation 1140 O'Brien Drive Menlo Park, California 9402 5 Attn: Dr. Morr i s Eisenberg

9

Elect r o -Optical Sy s tems , Inc . 300 North Halstead P. 0. Box 95085 Pasadena, California 91 107 Los Angeles, California 90045 Attn: E. Find1 Attn: L ibrary

Aerospace Corporation

Emhar t Manufacturing Company Box 1620 Hartford, Connecticut 06101 Attn: Dr. W. P. Cadogan

Engelhard Industries, Inc. 497 Delancy Street Newark, New J e r s e y 07105 Attn: Dr. J. G. Cohn

Dr. Arthur Fleischer 466 South Center Street Orange, New Je r sey 07050

General Elec t r ic Company Missi le and Space Division Spacecraft Department P. 0. Box8555 Philadelphia, Pennsylvania 191 01 Attn: E. W. Kipp, Room T-2513

General Elec t r ic Company Bat tery Products Section P. 0. Box 114 Gainesville, Florida 32601 Attn: Dr. R. L. Hadley

Ae r oj et -General Corporation Von Karman Center Building 312 / Department 31 11 Azusa, California 91 703 Attn: Russ Fogle

Aerospace Corporation Systems Design Division 2350 East El Segundo Boulevard El Segundo, California 90246 Attn: John G. Kr is i las

Allis -Chalmers Manufacturing Co. 11 00 South 70th Street Milwaukee, Wisconsin 532 01 Attn: Dr. P. Joyner

American University Mass. & Nebraska Avenues, N. W. Washington, D. C. 20016 Attn: Dr. R. T. Foley,

Chemistry Department

Arthur D. Little, Inc. Acorn P a r k C amb ridge , Mas sac hu s e t t s 0 2 1 4 0 Attn: Dr. E l le ry W. Stone

Atomics International Division North American Aviation, Inc. 8900 DeSoto Avenue Canoga Park , California 91304 Attn: Dr. H. L. Recht

Battelle Memorial Institute 505 King Avenue Columbus, Ohio 43201 Attn: Dr. C. L. Faus t

Aeronutronic Division Bell Telephone Lab, Inc. Philco Corporation Ford Road Attn: D. A. Feder , Rm.3B-294 Newport Beach, California 92660

Whippany, New J e r s e y 07981

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