RO- AI93 20 6 PREP RATION N D DE YLOP ENT OF DYRNCED flTTERYCRTALYSTS(U) EIC LADS INC NORWOOD MA M P KILROY ET AL.Si OCT 97 C-868 NSWC-TR-87-104 N6D921-86-C-D209

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AD-A193 208 /

PREPARATION AND DEVELOPMENT OF ADVANCED.BATTERY CATALYSTS

BY W. P. KILROY (NSWCIK. M. ABRAHAM AND M. ALAMGIR (EIC)

RESEARCH AND TECHNOLOGY DEPARTMENT

1 OCTOBER 1967

Apprond for public rmlems;dhtribution is unlimited.

D'TI

.4 NAVAL SURFACE WARFARE CENTERDahlgren, Virginia 22448-5000 0 Silver Spring, Maryland 20903-5000

88 4 11 258

- - - - - - - - - - 1K

UNCLASSIFIEDSECURITY CLASSI FICATlON OF TIS PAGE

REPORT DOCUMENTATION PAGEla REPORT SECURITY CLASSIl' CATION lb RESTF' CTIVE MARKINGS

UNCLASSIFIED #'~ (92a SE'jIYCA5 CTO U RT 3 DISTRIBUTION. AVAILABILITY OFRER

2b DECLASSIFICATION, DOWNGRADING SCHEDULE

4. PERFORMING ORGANIZATION REPORT NUMBER(S) 5 MONITORING ORGANIZATION REPORT NUMBER(S)

C-868 NSWC TR 87-104

6a NAME OF PERFORMING ORGANIZATION 6b: OFFICE SYMBOL 7a NAME OF MONITORING ORGANIZATION

EICLabratrie, Ic.(if applicable) Naval Surface Warfare Center___________________ Laboratories,_Inc White Oak Laboratory

5c. ADDRESS (City, State. and ZIP Code) 7b ADDRESS (City, State, and ZIP Code)

III Downey Street 10901 New Hampshire Avenu

Norwood, Massachusetts 02062 Silver Spring, Maryland 20903-5000

8a NAME OF FUNDING 'SPONSOPING T8b OFFICE SYMBOL 9 PROCUREMENT INSTRUMENT IDENTIFICATION NUMBERORGANIZATION j(if applicable) N60921I-86-C-0 209Naval Surface Warfare Center R33

Bc. ADDRESS (City, State, and ZIP Code) 10 SOURCE OF FUNDING NUMBERS

10901 New Hampshire Avenue PROGRAM PROJECT TASK WORK UjNITELEMENT NO NO NO IACCESSION NO

Silver Spring, Maryland 20903-5000 65502 411415-02 R76FAF

11 TITLE (include Security Classific ltbon)

Preparation and Development of Advanced Battery Catalysts

12 PERSONAL AUTHOR(S)

KilIroy, W. PL. (NSWC- Abraham, K. M. and Alamg ir, M. (EIC)_

13a TYPE OF REPORT 13b TIME COVERED 14 DATE OF REPORT (Year, Mll ,Dy)i PAGE COUNT

Interim Report FROM Aug 1986 ToFeb 1987 1987, October, I6 SJPPLEVEN4TARY NOTATION

17 COSATI CODES 18B SUBJECT TERMS (Continue on reverse if necessary and identify by block number)FIELD GROUP SUB-GROUP

07 04 ) Catalysis, Lithium Batteries,, Thionvl Chloride

'9 ABSTRACT (Continue on reverse if necessary and identify by block number)

SNew Catalysts wi ichI im pr o ve t he d -- Iia r ge( per f orna no:e c)1 1, i / S 0C 1 els i iV ii',

i den ti flied. 'Ilise caitlysts were obtained i)y thetrmal1 t riatment of a~th'haI ;ri

doped wi Lh the precuirsors, Co(N0j)7, manganese plithilocyanine (Nall~o) or vna~iiiur phtit 12

cya'ninir oxide (VOPc). The latter two mterials Ippear to be suiperior ti) k'I ' eItl lvst"presently avaitable for tiie in Li/S0C1' cellIs. Comlpared with ucI.lei 11 Y!-cont a ining ceil I s showed a I0 increase in- cellI capac:i ty aind a I () i ncwi t in iie I vi :i:

-at roomn teulperattisre . VOPc-cont aini ng cathodes incrieased thie cell capa it v hv in1,lu. I Ivoltngo bv 107" unde'r the' same cond itions. Thee of %'()1)( a-Is re nu t il I a t Iin Ii lprovimiunt s I I celIl per formance at l OW tenimperat iiri' s g e. at -o&'

20 D.STP'BL.T ON AVAILABILITY OF ABSTRACT 121 ABSTRACT SECURiTY CLASS F (AriON

0 UNLIID UNLIMITED CD SAME AS RPT [:iJ DTIC USERS I IN CILASS 1 F I El )

22a NAME OF RFSPONSIBLE INDIVIDUAL 22b TELEPHONE (include Area Code) 22( OFF CE SYV,3(iL

Will iam Ii. Ki lrov (20-2) 104-1 1 3 (Aide. K i )

DO FORM 1473, 84 VAR 83 APR elton may be used until exhausted SECURITY CLASSSFCATiON O)F 'HAS 'Ati,

All other editions are obsolete__

~~S" . I I I 1 2

NSWC TR 87-104

FOREWORD

This interim report describes some initial studies to evaluate new catalyticmaterials to improve the performance of high energy density, active lithiumbatteries.

This work is part of a collaborative effort between NSWC and EIC Laboratoriesto understand the fundamental mechanism of electrocatalysis in Li/SOC 2 cellsto improve their overall safety and to increase their performance to meetoperational requirements of new Navy mine batteries.

Funding for this effort was provided by the Office of Naval TechnologyHigh Energy Battery Technology Project (Mines Block), and the NSWC Navy SmallBusiness Innovative Research Program.

Approved y: /7"7 ' //" .I, ;

A!._:.3tln For WILLIA!-T.> ESSICK, Acting Head

:fT" ., 7A&I Materials Division

-,, ,,.

iii

NSWC TR 87-104

CONTENTS

Chapter Page

1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . 1

2 EXPERIMENTAL ............. .......................... 3

3 RESULTS AND DISCUSSIO3I .......... ..................... 5

DISCHARGE BEHAVIOR OF Li/SOC1 2 CELLS USING CATHODES

DOPED WITH COBALT CARBONYLS ..... ................. 26

DISCHARGE BEHAVIOR OF Li/SOC12 CELLS CONTAININGTRANSITION METAL COMPLEX-CATALYZED CATHODES ........... ... 26

MECHANISM OF ELECTROCATALYSIS IN Li/SOC1 2 CELLS ......... ... 33

4 CONCLUSIONS ........ ........................ ... 41

REFERENCES ......... ......................... .... 43

DISTRIBUTION ............. .......................... (1)

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NSWC TR 87-104

ILLUSTRATIONS

Figure Page

I DISCHARGE PLOTS OF LABORATORY Li/SOCI2 CELLSCONTAINING Co(N03)2-DOPED CATHODES, HEAT-TREATED AT 4000C, AND BASELINE CATHODE ...... ........... 7

2 DISCHARGE PLOTS OF LABORATORY Li/SOC12 CELLSCONTAINING Co(NO3)2-DOPED CATHODES, HEAT-TREATED AT 900 0C, AND BASELINE CATHODE ...... ........... 8

3 DISCHARGE PLOTS OF LABORATORY Li/SOCI 2 CELLSCONTAINING Co(N03)2-DOPED CATHODES, HEAT-TREATED AT 4000C, AND BASELINE CATHODE ...... ........... 9

4 DISCHARGE PLOTS OF LABORATORY Li/SOCI CELLSCONTAINING CATHODES DIPPED IN 7% Co(NO3 )2SOLUTION AND DRIED AT 130 0C, AND BASELINE

CATHODE ...................................... 105 DISCHARGE PLOTS OF LABORATORY Li/SOCI 2 CELLS

CONTAINING CoCO 3-DOPED CATHODES, HEAT-TREATED AT 9000 C, AND BASELINE CATHODE ............. . .. 11

6 DISCHARGE PLOTS OF LABORATORY Li/SOC1 2 CELLSCONTAINING CoCO 3-DOPED CATHODES, HEAT-TREATED AT 5000 C, AND BASELINE CATHODE ............. ... 12

7 DISCHARGE PLOTS OF LABORATORY Li/SOCI, CELLSCONTAINING 5 w/o Co2(CO)8 AS A CATHODEDOPANT WITH DIFFERENT HEAT TREATMENTS ............ ... 13

8 DISCHARGE PLOTS OF LABORATORY Li/SOCI., CELLSCONTAINING Col(CO)8 , SINTERED AT 300°,AS CATHODE DOPANT ...............................

9 DISCHARGE PLOT OF A LABORATORY Li/SOCL, CELLCONTAINING 5 w/o Co2(CO)8 , SINTERED AT2000 C, AS CATHODE DOPANT ..... .................. ... 15

10 DISCHARGE PLOTS OF LABORATORY Li/SOcl- CELLSCONTAINING Co,(CO)1 2, SINTERED AT 200°C, ASCATHODE DOPANT ............................... 16

11 DISCHARGE PLOTS OF LABORATORY Li/SOCI CELLSCONTAINING 5 w/o Co4 (CO)1 2, SINTERED AT6000C, AS CATHODE DOPANT AT DIFFERENT CUR-RENT DENSITIES .......... . .. ................ 17

12 DISCHARGE PLOT OF LABORATORY Li/SOCi 2 CELLSCONTAINING 5% VOPc-DOPED, AND BASELINECATHODES .......... .......................... . 18

13 DISCHARGE PLOTS OF LABORATORY Li/SOCI 2 CELLSCONTAINING 5% MnPc-DOPED, AND BASELINECATHODES .......... .......................... . 19

v

NSWC TR 87-104

ILLUSTRATIONS (Cont.)

Figure Page

14 DISCHARGE PLOTS OF LABORATORY Li/SOCI2 CELLSCONTAINING 5% CoPc-DOPED, AND BASELINECATHODES .......... .......................... .. 20

15 DISCHARGE PLOT OF A CELL CONTAINING 5% VOPc-DOPED CATHODE ........ ....................... . 28

16 DISCHARGE PLOT OF A CELL CONTAINING 5% MnPc-DOPED CATHODE ........ ....................... . 29

17 DISCHARGE PLOT OF A CELL CONTAINING 5% CoPc-DOPED CATHODE ........ ....................... . 30

18 DISCHARGE PLOT OF AN UNCATALYZED CELL ... ............ 3119 AMBIENT TEMPERATURE DISCHARGE PERFORMANCE OF

LABORATORY Li/SOCI 2 CELLS CONTAINING 5 w/o OFTHE Co-TAA-DOPED CATHODES PREPARED BY THE TEM1-PLATE SYNTHESIS ........ ...................... .. 32

20 IR SPECTRUM OF Co-TAA SYNTHESIZED BY THE CONVEN-TIONAL METHOD ........ ....................... .. 38

21 IR SPECTRUM OF Co-TAA PREPARED BY THE TEMPLATESYNTHESIS ......... ......................... . 39

v.

'

.5

S-S

NSWC TR 87-104

TABLES

Table Page

1 DISCHARGE RESULTS FOR Li/SOC12 CELLS CONTAININGCO(N03)2-DOPED CATHODES (DISCHARGE CURRENT IS210 mA (10 mA/cm2)] ........................... 6

2 DISCHARGE RESULTS FOR Li/50C19) CELLS CONTAININGCoCO, -DOPED CATHODES (CURRENT - 210 mA (10 mA!cm2 ? ) . .. .. .. .. .. .. .. .. .. .. ... .. .... 21

3 DISCHARGE RESULTS FOR Li/S0C12 CELLS CONTAINING

Co2(CO)8-DOPED CATHODES [CURRENT =210 mA(10 mA/cm2) EXCEPT WHERE NOTED] .. ................ 2

4 DISCHARGE RESULTS FOR Li/S0C12 CELLS CONTAININGCo (CO)12-DOPED CATHODES [CURRENT = 210 mA (10 mA!cm ) EXCEPT WHERE NOTED]. ................. . 23

5 DISCHARGE RESULTS FOR Li/S0C1, CELLS CONTAININGTRANSITION METAL COMPLEX-DOPED CATHODES

*DISCHARGED AT ROOM TEMPERATURE. .................. 24

6 DISCHARGE RESULTS OF Li/S0C12 CELLS CONTAINING(5%) TRANSITION METAL COMPLEX-DOPED CATHODESAT -300C AT 10 mA/cm 2 . . . . . . . . . . . . . . . . . . . . . . . 25

7 X-RAY DATA FOR THE UNDISCHARGED CATHODES COLN-TAINING THE VARIOUS DOPANTS. .... ......... . . . .

8 X-RAY DATA FOR THE CATHODE OF A Li/S0C12 LABORA-TORY CELL CONTAINING 5 w/o VOPc AS CATHODEDOPANT AND DISCHARGED AT 10 mA/cm2 . . . . . . . . . . . . . . . 35

9 X-RAY DATA FOR THE CATHODE OF A Li/SOd]., LABORA-TORY CELL CONTAINING 5 w/o MnPc AS CATHODE

* DOPANT AND DISCHARGED AT 10 mA/cm2 . . . . . . . . . . . . . . . 36

vii/viii

--------

XSWC TR 87-104

CHAPTER 1

INTRODUCTION

The search for catalysts to improve the discharge performance and safety ofthe Li/SOCl2 cell is being actively pursued at NSWC. Data available to date -7

indicate that the power capabilities of the Li/SOCI2 cell can be improved tovarying degrees in the presence of cathode catalysts. A variety of materials,,4hen incorporated in the carbon cathode or added to the electrolyte, have beenfound to increase cell discharge potentials and provide hilher capacities at highrates. Some of these materials include finely divided Pt, Cu powder, 6 metalphthalocyanine and related macrocyclic complexes,1 ,2 ,4 and tetracyanoethylene andacetylacetonate complexes of Co and Fe. 7 Two of the most promising catalystshave been the Fe-phthalocyanine (FePc) complex, 1,4 and the Cobalt-dibenzotetra-azaannulene (Co-TAA) complex, 11.1,2

N

I, Fe-phthalocyanine II, Cobalt-dibenzotetraazaannulene

Despite empirical observations of improved discharge behavior and bettersafety characteristics of Li/SOC12 cells containing cathodes doped with catalysts,our present understanding of the mechanism of electrocatalysis in this cell isinadequate. This lack of knowledge of the mechanism is evident in the followingexplanations given by different researchers concerning the discharge mechanism ofcatalyzed Li/SOCl2 cells.

e Doddapaneni4 initially suggested that FePc changes the mechanism of theSOC12 discharge reaction and that the increased capacity was due to the reductionof S02 to Li2S204. However, no analytical work was carried out to verify this.Additional quantitative work is required to support this claim.

* Walsh and Yaniv suggested that the discharge mechanism in Co-TAA catalyzed

cells is different from that in the uncatalyzed cells. They maintained that the finaldischarge products are LiCI, solvated Li.,O, and S, and since no SO' is formed accordingto this mechanism, the cells are safer. -However, little analytical data were pre-sented to substantiate this claim. Our studies on tbe discharge products from Co-TAA

1

leK

NSWC TR 87-104

catalyzed Li/SOCI2 cells showed no evidence of Li20 upon analysis by X-ray diffrac-tion and FTIR spectroscopy. 1 The X-ray diffraction pattern of discharged cathodesshowed LiCI and S. FTIR analysis of the gaseous products from discharged cellsshowed that SO2 is a discharge product in Co-TAA catalyzed cells. Additionalanalyses are needed to quantitatively determine the discharge products andresolve these different findings.

Clearly, the present understanding of the mechanism of electrocatalysis inLi/SOCI2 and related cells is poor. Because of the lack of understanding of themechanism of catalyst-assisted discharge reactions, systematic design of catalystsfor the Li/SOC1 2 cell cannot be accomplished without additional studies.

The eletrocatalytic activity of CoO, Co304 , or Co towards the reductionof SOC12 was investigated to see if the actual catalyst species in the Co-TAAor CoPc impregnated cathodes might be one or more of these oxides, or finelydivided Co. In the preparation of Co-TAA- or CoPc-catalyzed carbon cathodes,carbon black containing the complexes is heat treated at 500 to 600*C.2,4 Atthese temperatures, the metal macrocyclic complexes undergo decomposition givingoff volatile organic fragments.9-11 The residues left behind have been claimedto have varying compositions. It is believed that Co-TAA decomposes in a step-wise fashion when heated. At ~400*C, Co-TAA gives off hydrogen to form whatappears to be a polymeric material. At higher temperatures, e.g., -550*C, asubstantial loss of carbon and hydrogen along with some nitrogen occurs. Atabout 800*C there is evidence of complete decomposition of Co-TAA to give metal-lic cobalt as the residual product. Cobalt oxide (CoO) is also believed to be acomponent of the residue obtained from the decomposition of Co-TAA. The latterapparently is formed by the reaction of the initially-formed, finely-divided Cowith oxygen.

Knowledge of the actual composition of the catalyst is important. Oxidesare less expensive and easier to prepare than macrocyclic complexes. Certainlimitations of the present transition metal complex catalysts, such as theirinstability in SOCI2/LiA1C14 or poor high temperature storability of cells, maybe overcome with improvements brought about by the knowledge of the actual compo-sition of the catalyst species. It is believed that some of these limitationsarise from reactions associated with the organic moiety in the complex. There-fore, eliminating the organic moiety from the catalyst center may result inoverall improvements in cell performance.

2J

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NSWC TR 87-104

CHAPTER 2

EXPERIMENTAL

Our scheme for preparing catalyzed carbon cathodes involved treatment ofacetylene black carbon with appropriate precursors followed by heat treatment atvarious temperatures. The chemical reactions that were used to deposit cobaltoxides and finely divided Co in the carbon are depicted in equations (1-4).

CoC03 5000C COO + C02 (1)

3Co(N03 )2 400C 0Co30 4 + 6N0 2 + 02 (2)

Co2 (CO)8 -200 Co + CO (3)200° C

Co4 (CO)12 - 4Co + 12C0 (4)

Three transition metal phthalocyanine complexes have also been evaluated..These are cobalt phthalocyanine (CoPc), manganese phthalocyanine (MnPc), andvanadium phthalocyanine oxide (VOPc). All these metal complexes are commerciallyavailable and their synthesis is rather straightforward. In addition, we haveattempted to prepare Co-TAA by simpler synthetic routes and evaluate its cata-lytic performence.'12

The precursors used for preparing cobalt oxide-catalyzed cathodes wereCo(N03)2 and CoCO 3 . Acetylene black carbon was first doped with the precursorsand then sintered at various temperatures prior to fabricating the electrodes.Co(N03)2 was incorporated into the carbon in an aqueous medium. Solutions inwater containing required amounts (5, 10, and 20 w/o) of Co(N03 )2 were mixed wellwith carbon, dried at 100*C and the mixture was heat treated at 400 or 900*C underflowing argon.

In order to incorporate COC0 3 , a slurry of CoCO 3 in ethanol/H 20 was mixed

with carbon, dried at 100*C and then s!ntered, in argon, at 500 or 9000C.l 3

Teflon-bonded carbon electrodes were made with doped cathodes. The Li/SOCl 2laboratory cells used for these studies consisted of a cathode sandwiched betweentwo Li anodes (15 mil thick) pressed onto Ni screens. The cells were filled with4.0 ml, 1.8M LiLIC 4/SOCI2 electrolyte solution and were truly carbon-limited. ALi strip was also incorporated into the cell as a reference electrode. Typically,the cathodes were 3.5 cm x 3.0 cm x 0.10 cm, and the geometric surface area was21 cm2 . The cells were discharged galvanostatically.

3/4

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NSWC TR 87-104

CHAPTER 3

RESULTS AND DISCUSSION

Discharge results obtained with Co(N0 3)2 catalyzed cells are summarized inTable 1. The capacity in an uncatalyzed cell, hereafter referred to as baselinecell, at 10 mA/cm 2 at room temperature corresponded to a carbon utilization of1.36 Ah/g. Figures I through 14 illustrate discharge behavior of the doped cellscompared to a baseline cell whereas Tables i through 6 show the capacity normalized(Ah/g carbon) to account for the varying masses of carbon used in each cell. Cathodescontaining 5% Co(N03 )2 , sintered at 400*C, and those first dipped in a Co(N0 3 )2solution followed by a heat treatment at 130*C show evidence of catalyticactivity. In Cell No. 1, containing 5 percent Co(N03)2-doped cathode, the carbonutilization was 1.59 Ah/g or a 17 percent improvement over the uncatalyzed cell.It appears that the catalytic activity is extremely sensitive to the thermaltreatment of the carbon. Figures I and 2 compare the behavior of the Co(NO3 )2doped cells with the baseline cathodes. The Co(N03)2-doped cathodes, whethersintered at 400 or 900*C, showed no catalytic activity at -30*C as illustrated inFigure 3. A close examination of the data for Cells 3 and 4 in Table 1 showsthat the apparent lack of catalytic activity in cathodes doped with 10 percentand 20 percent Co(N03 )2 may be due to a decrease in th total available SOC1 2 atthe electrode active sites, because the excess catalyst begins to occupy signifi-cant fractions of pore volume. The mass-transport in the cathode is impeded ascha,..,els are blocked. The observed capacities of Cells 3 and 4 agree with thisexplanation because the capacity of Cell 3 is -85 percent and that of Cell 4 is-77 percent of the capacity of Cell 1. The decrease in capacity in each cellcorresponds approximately to the amount of catalyst added beyond 5 percent.

The behavior of the carbon electrodes that were dipped in Co('10 3 )2 solutionfollowed by drying at 130C is illustrated in Figure 4. These electrodes exhibithigher voltages than the electrodes sintered at 4000 C, and their capacities aresimilar to those sintered at 900°C.

A comparison of the behavior of Co(NO3)2-containing electrodes heat treatedat 400 and 1300 C, presented in Figures I and 4, suggest that in the latter casethe active species probably is Co(N03 )2 itself while in the former case it is anoxide, probably Co304 . Although the capacity of the cathode is increased as aresult of Co304 doping, the cell discharge potential remains the same as that in

* the baseline case. When Co(N03)2 itself is the active catalyst species, the celldischarge voltage is slightly enhanced while the capacity of the cathode shows adecline.

Further studies of these electrodes, especially with respect to optimizationof the amount of Co(NO3) 2 and the sintering temperature, are warranted because ofthe promising results from Co(N0 3)i doping. This will be carried out in futurestudies.

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NSWC TR 87-104

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a.

TABLE 6. DISCHARGE RESULTS OF Li/SOCI, CELLS CONTAINING (5%)TANSITION METAL COMPLEX-DOPED CATHODES AT -30

0C AT 1O mA/cm 2

Capacity, Ah/g

Cell Mid-DischargeNo. Complex Voltage, V (2.OV) (0.OV)

37 VOPc 2.74 0.91 0.97

38 CoPc 2.81 0.51 0.57

39 MnPc 2.71 0.58 0.64

Baseline 2.60 0.70 1.0cathode withoutcatalyst

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NSWC TR 87-104

The discharge results obtained by using CoCO 3 as the catalyst precursors aresummarized in Table 2. Relevant discharge curves are presented in Figures 5 and6. The discharge capacities are similar to or less than that obtained in thebaseline cell. CoCO3 doping seems to decrease the capacity of the baseline elec-trode in proportion to the amount of the added dopant. X-ray analysis of CoC0 3-doped carbon after heat treatment showed the presence of cobalt carbides and Co304(discussed later). It appears that cobalt carbides have little or no catalyticactivity on the reduction of SOCd2 .

,p.,

DISCHARGE BEHAVIOR OF Li/SOC12 CELLS USING CATHODES DOPED WITH COBALT CARBONYLS

As mentioned earlier, the reasoning behind the use of cobalt carbonyls ascatalyst precursors has been the incorporation of finely divided metallic cobaltin the carbon cathode.14 It is possible that such electrodes may also containcobalt carbides or oxides, the former being formed during heat treatment of thecarbonyl and the latter during reactions following the heat treatment withatmospheric oxygen.

Discharge data for cells using cobalt carbonyl-doped cathodes, heat treatedat various temperatures, are summarized in Tables 3 and 4. Co2 (CO) 8 was depos-ited on the carbon from a THF solution and Co4 (CO)12 from a diethyl ether medium.After the carbon was mixed with the respective solutions, the solvent was removedby pumping under a vacuum. The carbon deposited with the cobalt carbonyl washeat treated in Ar at the various temperatures indicated in Tables 3 and 4.Typical discharge curves obtained with these carbon electrodes are given inFigures 7 through 11. Carbon utilization data are presented in Tables 3 and 4.Neither the Co2(CO)8-doped nor the Co4 (CO)12-doped electrodes showed any Nevidence for catalytic activity.

DISCHARGE BEHAVIOR OF Li/SOCI 2 CELLS CONTAINING TRANSITION METAL COMPLEX-CATALYZEDCATHODES

Transition metal complexes that haie so far shown the highest activity inLi/SOCl2 cells are the phthalocyanine (Pc) complexes of Co and Fe, and Co-TAA.FePc was found to be soluble in SOC12/LiAlCl4 and, therefore, its use is limitedto reserve cells. The cobalt and iron phthalocyanines have apparently been cho-sen previously for use as catalysts in Li/SOC12 cells because of their ability tocatalyze the reduction of oxygen in fuel cells. Based on that criterion MnPc andVOPc should not function as active catalysts for SOC1 2 reduction, since they donot catalyze the reduction of oxygen well. Thus the use of MnPc and VOPc pro-vided a test for the selection criteria of catalysts for use in the Li/SocI 2 cellon the basis of their catalytic activity in fuel cells.

The phthalocyanines were dissolved in concentrated H2SO4 . Acetylene blackcarbon was mixed intimately with this solution and later washed with distilledwater until the pH of the washings became neutral. The mixture was heat treatedat 600°C under flowing Ar. Cathodes were fabricated in the usual way by mixingwith Teflon binder followed by drying and sintering at 300*C in Ar atmosphere.The discharge results obtained at 10 mA/cm2 at room temperature are summarized inTable 5.

26

NSWC TR 87-104

Figure 12 depicts the discharge plot of a cell containing 5 percent VOPc.The load voltage is 3.35V. The capacity to 0.OV amounted to 1.98 Ah/g. The loadvoltage of the cell containing 10 percent VOPc was slightly lower but the cathodeutilization was similar. VOPc shows a 45 percent improvement in capacity and a10 percent improvement in cell voltage, both at 10 mA/cm2 .

The discharge behavior of a laboratory cell containing 5 percent MnPc-dopedcathode is illustrated in Figure 13. The load voltage of this cell is about 50 mVlower than that of the VOPc containing cell; however, the capacity is higher. Thecell containing a 10 percent load of MnPc performed worse than that containing5 percent MnPc. It appears that the amount of catalyst is more critical with MnPcthan with VOPc. The performance improvement attained with MnPc is a 60 percentincrease in capacity and -10 percent increase in cell voltage. The performance ofMnPc at room temperature surpasses that of CoPc which we have evaluated to checkthe validity of our procedure. The discharge curve for the Li/SOCI2 cell con-taining CoPc catalyzed cathodes is given in Figure 14. The performance we haveachieved with CoPc is similar to what has been reported in the literature.4

Cells using cathodes which contained 5 percent loads of CoPc, VOPc, and MnPcwere also discharged at -30*C, at a current density of 10 mA/cm2 . The resultsare summarized in Table 6. Discharge curves are presented in Figures 15 through18. All the catalyzed cells showed higher mid-discharge voltages than the base-line cell. The VOPc catalyzed cell exhibited the best performance. The voltageregulation, compared with the baseline cell, was excellent, yielding practicallyall the capacity at a constant potential. This is extremely significant, sinceuncatalyzed cells usually dxhibit a downward sloping potential profile at lowtemperatures, yielding a significant fraction of the capacity at potentials below2.OV; Figure 18.

Cells containing CoPc and MnPc catalyzed cathodes also showed better voltageregulation at -30*C (Figures 16 and 17). However, their capacities were somewhatlower than that of the baseline cathode.

The preliminary results obtained so far with transition metal complex cata-lyzed cathodes indicate that MnPc is the preferred catalyst from the standpointof performance at room temperature, while VOPc is the preferred material forapplications involving both room and low temperatures. On the other hand, it ispossible that a mixture of VOPc and MnPc might be the best catalyst compositionfor superior cell performance at both room and low temperatures.

We have also carried out discharges of Li/SOCd2 cells containing cathodesdoped with 5 w/o Co-TAA. This Co-TAA was synthesized by a different procedure1 2

than the material previously reported.1 ,2 It showed a slightly different IRspectrum than the previous material (discussed later). Co-TAA was dissolved in

dimethyl formamide (DMF) (1 ml DMF/l.5 mg Co-TAA) and mixed with Shawinigan acet-ylene black carbon. DMF was removed by heating the mixture at 70*C under vacuum.Cathodes were made by blending the dried carbon-Co-TAA mix with 10 w/o Teflonbinder and spreading it onto Ni screens. After drying overnight at 100*C toremove water, the cathodes were sintered at 300*C for 20 minutes under flowing Ar.

The discharge performance of Co-TAA catalyzed laboratory Li/SOCI 2 cells atroom temperature and at two different rates is illustrated in Figure 19. At 5and 10 mA/cm2 discharge rates, the cathode utilizations were 2.02 and 1.75 Ah/g,

27

NSWC TR 87-104

* -300C* 210 MA (10 MA/cM2 )

3

2

0 _

1 I "

20 40 60 80 100 120

TIME, MINS.

5-

FIGURE 15. DISCHARGE PLOT OF A CELL CONTAINING 5% VOPc-DOPED CATHODE

2.8-.

5-

'-

5.

.5

28 71.=

.$.

NSWC TR 87-104

-300c4m.210 MA (10 MA/CM2)%

> 3

wwLuu

S 2

-J

0

F20 40 60

TIME, MINS.

FIGURE 16. DISCHARGE PLOT OF A CELL

CONTAINING 5% MnPc-DOPED

CATHODE

" 29 -

NSWC TR 87-104

4 -300c

* 210 MA (10 MA/CM 2 )

2P

I-

I S

20 40 60 80TIME, MINS, "

FIGURE 17. DISCHARGE PLOT OF A CELL CONTAINING5% CoPc-DOPED CATHODE

Wk

. 5

..

3.

30 --

g~i

NSWC TR 87-104

4* -30 0C210 MA (10 MA/CM 2)

W3

-j 2 ell

0 I20 40 60 80 100 120

TiME, MINS.

FIGURE 18. DISCHARGE PLOT OF AN UNCATALYZED CELL

31S

NSWC TR 87-104

z

0

0 z

CN

C-C,

5,u w

0L C.

00-

CN

U 00.

CL~Z:-

u.J (n

u.J

'30VIIOA a:1

32

NSWC TR 87-104

respectively. The average load potential of these cells at 5 mA/cm2 was 3.37V,while that at 10 mA/cm2 was 3.2V.

MECHANISM OF ELECTROCATALYSIS IN Li/SOCI2 CELLS

Our tentative model for electrocatalysis in Li/SOCI2 cells is schematicallyillustrated below. This scheme suggests the formation of an adsorption complexbetween SOC1 2 and the catalyst, followed by reduction of the complex, and desorp-tion of the reduction products. The actual mechanism might be more complex thanthe one illustrated. Considerable experimental data are required to fully eluci-date the mechanism of electrocatalysis in Li/SOC1 2. It also remains to beestablished whether the same mechanism can explain catalysis by all catalyststhat have so far been identified.

Electrodt containing catalystIWAK /-1SOCSC(SOCC2) ad$

Cat( C) as Cat a

Cat (SOC L2 ads

X-ray analysis of the catalyzed cathodes was performed before and aftertheir use in Li/SOC12 cells. The results are presented in Tables 7 to 9.

The X-ray data for the various catalyst-doped cathodes given in Table 7 showthat only with CoCO 3 precursors could any assignment of the catalyst species bemade. The X-ray data seem to indicate that several cobalt carbides and Co304 areformed in the thermal treatment of the CoCO 3 impregnated carbon. The transitionmetal macrocyclic complex catalyzed cathodes only show the carbon lines. However,the X-ray data strongly suggest that these cathodes do not contain any oxides orcarbides as the peaks for those species are absent. These analyses were performedwith 10 percent doped electrodes. At such low levels of catalyst, poorly crystal-line materials will escape detection. X-ray analysis on carbon doped with higherlevels of catalyst will be performed in the near future.

The data in Tables 8 and 9 indicate that in the case of VOPc and MnPc cataly-sis, LiCl is a discharge product. Because these cells are flooded, most of the Swould go into solution, thereby escaping detection by X-ray. The strongest S lineis present in the X-ray patterns of the MnPc catalyzed cathode. Clearly, thesedata are insufficient to draw a picture of the mechanism of electrocatalysis.However, the absence of Li20 suggest that no significantly difterent products fromthose formed in baseline cells are probably formed. Further analysis, includingquantitative analysis of CI-, S, and SO2 will be performed in future studies.

33

',,' ,TV,?~v.%, ? .'?.. ,*,*5TQ.'-S .'%* Sh .- '<< :v:'".?. : ;

NSWC TR 87-104

TABLE 7. X-RAY DATA FOR THE UNDISCHARGED CATHODESCONTAINING THE VARIOUS DOP.ANTS

SinteringDopant Level Temperature

(wt %) (0C) d, A I/Io Assignment

20% CoCO 3 500 7.34 100 Carbon4.85 50 Carbon

2.45 45 Co2 C, Co3 C, Co3042.12 68 Co2 C, Co 3 C1.48 30

20% Co(NO 3 )2 900 7.41 100 Carbon

4.91 35 Co(NO3 )2, Carbon

10% VOPC 600 7.34 100 Carbon

4.88 17 Carbon3.46 Trace Carbon

10% MnPc 600 7.34 100 Carbon

4.85 23 Carbon

3.17 13

5Z Co?c 600 7.34 100 Carbon

4.86 30 Carbon

10% Co4 (CO) 12 200 7.34 100 Carbon

3.59 601.95 30

'4PI,.-,

34

+. .. . . .. . . . . . . . . ... . ,,4

I. 1.,- ,t.- , - - - - . " , _ -, t, + "- - ,, "I- k I

NSWC TR 87-104

TABLE 8. X-RAY DATA FOR THE CATHODE OF A Li/SOC1 2 LABORATORY

CELL CONTAINING 5 w/o VOPc AS CATHODE DOPANT ANDDISCILARGED AT 10 mA/cm 2

J 0

4' dA I/Io Assignment

3.85 Trace S2.97 100 LiCI2.58 90 LiCI1.83 60 LiCI1.56 30 LiCI

1.48 10 LiCI1.29 Trace LiCi1.18 10 LiCI

1.15 10 LiCI1.05 10 LiCI

0.99 10 LiCI0.91 Trace LiCI l

0.87 Trace LiCI0.86 Trace LiCl ,0.82 Trace LiCI

35

NSWC TR 87-104

TABLE 9. X-RAY DATA FOR THE CATHODE OF A Li/SOC. LABORATORYCELL CONTAINING 5 w/o MnPc AS CATHODE DOPANT AND

DISCHARGED AT 10 mA/cm 2

I/I Assignment

4.81 Trace C3.85 20 S3.47 Trace3.20 Trace LiAICI43.08 Trace

2.97 100 LiCI2.84 Trace LiAICI 42.73 902.57 90 LiCI2.42 Trace

2.29 101.93 101.87 Trace LiA1C1 4

1.82 50 LiCI1.73 Trace LiAIC 14

1.57 201.55 30 LiCl1.46 20 LiCl1.36 Trace1.29 Trace LiCI

1.22 Trace1.18 10 LiCI1.15 20 LiCI1.05 20 LiCI1.03 Trace

0.99 20 LiC10.87 20 LiCI0.86 20 LiCI-0.81 10 LiCI l

36

NSWC TR 87-104

The IR spectrum of Co-TAA prepared by two different methods is illustrated Oin Figures 20 and 21. Comparison of these spectra reveal that Co-TAA as preparedby Reference 2, and previously discussed in Reference 1, is possibly somewhat ndifferent from that prepared by the template synthesis described in Reference 12. .%.

Studies to evaluate these differences are in progress.

",

.3

'p

'p"%

%-p .

2-'-p.

S

37 ."

p ~ p *j. .V-w w %.. ~ - ~ * -- ~- . .,. .

NSWC TR 81-104

CDC

go0-L

>

CDC

NC

Ln .n

C) C>a

NOISSISNV~iw

38~

NSWC TR 87-104

E--

C)E-

Q

w S.

a N.

(D0 .0 0

LIN

Lr) C 00 t

39/40

NSWC TR 87-104

CHAPTER 4

CONCLUSIONS

Doping acetylene black carbon with cobalt species generated by the thermaldecomposition of CoC0 3 , Co2(CO) 8 , and Co4 (CO)1 2 did not result in cathodes suit-able for catalyzing the discharge reaction of the Li/SOCI2 cell. X-ray analysisrevealed that CoCO 3 impregnated carbon generates cobalt carbides and Co304 uponthermal treatment at 5000 C. The dopant species derived from Co2 (CO)8 and Co4 (CO) 12could not be identified by X-ray.

Mixing acetylene black with Co(N03 )2 followed by thermal treatment resultedin increased capacity for the electrode. The cell voltage remained the same as inbaseline Li/SOCI2 cells. Further studies, especially with regard to the amountof Co(N03)2 and optimum temperature for thermal treatment, are needed.

Acetylene black carbon impregnated with transition metal phthalocyanines,follnwed by sintering at 600°C, resulted in highly enhanced capacity and highercell voltage for the high rate discharge (viz., 10 mA/cm 2) of Li/SOCI2 cells. Twonew catalysts, VOPc and MnPc, have been discovered. These catalysts appear to besuperior to many of the catalysts presently available. MnPc-containing cathodesshowed a 60 percent increase in capacity and a 10 percent increase in cell vol-tage at 10 mA/cm2 at room temperature. VOPc-containing cathodes increased thecell capacity by 45 percent and cell voltage by 10 percent at 10 mA/cm2 at roomtemperature. VOPc also improved cell performance significantly at -300 C.

Currently available data indicate that transition metal macrocyclic complexeshave special features that allow catalytic activity for the discharge of Li/SOC 21cells. The fact that VOPc and MnPc are highly active for SOC1 2 reduction, whileinactive in fuel cells for 02 reduction, suggests that the criteria for selectionof catalysts for the reduction of SOC12 are different from those in fuel cells.

MnPc, VOPc, an CoPc were incorporated into the carbon by heating at 600*C.At these temperatures, these complexes are known to decompose. Questions remainabout the nature of the active catalyst species when phthalocyanines are used.X-ray analysis did not provide the necessary answers because of the low concen-trations of the catalyst species. Further work is planned.

Limited analyses of discharged cathodes seem to suggest that the dischargeproducts are most probably LiC, S02 , and S, as in uncatalyzed cells. Quantita-tive analysis remains to be performed.

The new catalysts VOPc and MnPc appear to be of considerable potential forpractical use. Therefore, further studies exploring the full extent of the use-fulness of these new catalysts in practical batteries should be performed.

41

NSWC TR 87-104

Additional studies are required to explain any differences in the catalysisprocess arising from samples reported to be Co-TAA but, as indicated by IR data,possibly differ in structure.

I

42

VI

NSWC TR 87-104

REFERENCES

1. Abraham, K. M.; Pitts, L.; and Kilroy, W. P., J. Electrochem. Soc., Vol. 132,

1985, p. 2301.

2. Walsh, F. and Yaniv, M., ERADCOM Technical Report, DELET-TR-83-0386-F, May1984 (also refer to paper to be given by D. Barinelli and F. Walsh at

33rd Power Sources Symposium, Cherry Hill, NJ, Jun 1988)•

3. Schlaikjer, C. R., Chapter 13 in Lithium Batteries, J. P. Gabano, Ed.,Academic Press, 1983. S

4. Doddapaneni, N., Proceedings of the 31st Power Sources Symposium, Cherry Hill,NJ, The Electrochemical Society, p. 411, 1984.

5. Klinedinst, K. A., J. Electrochem. Soc., Vol. 128, 1981, p.'2504.

6. Behl, W. K., J. Electrochem. Soc., Vol. 128, 1981, p. 939.

7. Klinedinst, K. A. and Gary, R. A., U.S. Patent 4,452,872.-"

8. Abraham, K. M. and Alamgir, M., J. Electrochem. Soc., Vol. 124, 1987, p. 258.

9. Scherson, D. A. et al., Electrochim. Acta, Vol. 28, 1983, p. 1205.

10. Wiesener, K., Electrochim. Acta, Vol. 31, 1986, p. 1073.

11. Jahnke, H.; Schonborn, M.; and Zimmermann, G., Topics in Current Chemistry,Vol. 61, 1976, p. 133.

12. Chave, P. and Honeybourne, C. L., Chemical Communications, 1969, o. 279.

13. Krustinsons, J., Z. Elektrochem., Vol. 39, 1933, p. 936.

14. The Handbook of Chemistry and Physics, The Chemical Rubber Company Press,63rd Edition, 1983.

43/44 I

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Hughes Aircraft Company Cordis CorporationAttn: Dr. L. H. Fentnor 1 Attn: W. K. Jones 1Aerospace Groups P. 0. Box 525700Missile Systems Group Miami, FL 33152Tucson Engr LaboratoryTucson, AZ 85734 Tadiran

Attn: M. Babai 1Lockheed Missiles & Space Co., Inc. P. 0. Box 75Attn: Library 1 Rehovot, IsraelLockheed Palo Alto Rsch Lab F3251 Hanover Street Power Conversion, Inc.Palo Alto, CA 04304 Attn: Dr. T. Reddy

495 BoulevardDuracell International, Inc. Elmwood Park, NJ 07407Attn: B. McDonald 1Battery Division Covalent Associates, Inc.South Broadway Attn: Dr. V. Koch 1Tarrytown, NY 10591 52 Dragon Court

Woburn, MA 01801Duracell International, Inc.Attn: W. Bowden 1 MoLi Energy Limited

A. N. Dey 1 Attn: Dr. J. A. Stiles 1F. Parsons 1 4010 Myrtle StreetLibrary 1 Burnaby, BC V5C 4G2 Canada

Duracell Research Center37 A Street ECONeedham, MA 02194 Energy Conversion

Attn: Dr. F. M. Walsh 1Boeing Aerospace Company 225 Needham StreetAttn: S. Gross 1 Newton, MA 02164

C. Johnson 1P. 0. Box 3999 Ansum Enterprises, Inc.Seattle, WA 98124 Attn: Dr. S. ?. Wolsky

950 DeSoto RoadElectrochimica Corporation Boca Raton, FL 33432Attn: M. Eisenberg 12485 Charleston Road Advanced Battery G.oupMt View, CA 94040 Attn: Dr. R. M. Murphy

269 Westwood RoadEltron Research Lancaster, NY 14086Attn: T. Sammells 1710 East Ogden Avenue Medtronics, Inc.Naperville, IL 60540 Attn: Dr. D. Untereker

6700 Shingle Creek ParkwaySaft America, Inc. Brooklyn Center, MN 55430Attn: Dr. R. J. Staniewicz 1

Dr. K. Press IDr. G. AIllvey 1

107 Beaver Court

Cockeysville, MD 21030

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NSWC TR 87-104

DISTRIBUTION (Cont.)

Copies copies

ELTECH Systems Corporation Amoco Corporation

Attn: D. E. Harney 1 Attn: Dr. J. N. Gleeson 1Research & Development Center Amoco Research Center625 East Street P. 0. Box 400Fairport Harbor, OH 44077 Naperville, IL 60566

Harkness Consultants Inc. Power Information CenterAttn: Dr. A. C. Harkness i CSR, Inc.Suite 1601 1400 Eye Street, N.W.

150 - 24th Street Suite 600West Vancouver, BC V7V 4G8 Canada Washington, DC 20005 1

Dr. Boone B. Owens 1 Internal Distribution:A%

P. 0. Box 8205 E231 2St. Paul, MN 55108 E232 15

E35 1Ultra Technologies - KODAK R33 (W. P. Kilroy) 50Attn: P. F. Dickinson 1P. 0. Box 267Rt. 88 SouthNewark, NY 14513

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