nswc tr - dtic
TRANSCRIPT
NSWC TR
06-390
SAFETY EVALUATION OF THE EXPENDABLESO JND VELO%.-TIY PROBE (SSXSV)
By J. . BAKER J. A. EARNES R. F, BIS P.B. DAVIS L. A. KOWALCHIK
RESEARCH AND TECHNOLOGY DEPARTMENT
AUGUST 1986
DTIC
Approved for public rulewe;distribtution is unliited. D
t NAVAL SUVFACE WEAPONS CENTER6 2ahlhwrn, VWrginia 22448-5000 0 Silver Spring, Ma•Iand 2G9035000
UNCI AS SIFI;E D p% • / •a'i / .ECURITY CLASSFICATION OF THIS PAGE / / 7
REPORT DOCUMENTATION PAGEIa. REPORT SECURITY CLASSIFICATION lb RESTRICTIVE MARKINGSUNCLASSIFIED
2a, SECURITY CLASSIFICATION ",UTHORITY 3 DISTRIBUTION /AVAILABILITY OF REPORTApproved for public release; distribution
2b- DECLASSIFICATION/DOWNGRADING SCHEDULE is unlimited
4. PERFORMING ORGANIZATION REPORT NUMBER(S) 5 MONITORING ORGANIZATION REPORT NUMBER(S)
NSWC TR 86-390
Sa. NAME OF PERFORMING ORGANIZATION Ob. OFFICE SYMBOL 7a NAME OF MONITORING ORGANIZATION
Naval Surface Weapons Center R39f pplicable)
6c. ADDRESS (City, State, and ZIP Code) 7b. ADDRESS (City, State, and ZIP Code)
10901 New Hampshire Ave.Silver Spring, MD 20903-5000
"$a. NAME OF FUNDINCG/SPONSORING 8b. OFFICE SYMBOL 9. PROCUREMEN.T INSTRUMENT IDENTIFICATION NUMBERORGANIZATION (If applicable)
Bc. ADDRESS (City, State, and ZIP Code) 10. SOURCE OF FUNDING NUMBERSPROGRAM PROJECT TASK WORK UNITELEMENT NO. NO. NO ACCESSION NO.
11. TITLE (Include Security Classification
R
Safety Evaluation of the Expendable Sour.d Velocity Probe (SSXSV)
12. PERSONAL AUTHOR(S)alep r .- A J -_ -" RA r n p r, .7 A -" R i c R V -_ n A ri s_Q 1P . R _ _ Alta h ile T. A ,
13a. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Year, Month, Day) S. PAGE COUNTFROM TO 19Rf A,,vmt 27
16. SUPPLEMENTARY NOTATION
17. COSATI CODES 18. SUBJECT TERMS (Continue on reverse if necessary and identify by block number)FIELD GROUP SUB-GROUP Lithium PX28L Battery Safety
Duracell DL- Manganese Dioxide
19. ABSTRACT (Continue on reverse f necessary and identify by block number)
* The Arctic Submarine Laboratory, Naval Ocean Systems Center, San Diego, sought approvalcarry the Expendable Sound Velocity Probe (SSXSV) on board submarines. The battery used bythe SSXSV employs a lithium/manganese dioxide couple. The battery- is assembled.., the SSXSVsupplier - Sippican Ocean Systems, Inc. - from a Duracell PX28L battery and a •L•Njell. TheNaval Surface Weapons Center, White Oak, conducted a safety evaluation of the/7 SV asrequired by NAVSEA Notice 9310. This report presents the results of the safety evaluation othe SSXSV.
.. L
20. DISTRIBUTION IAVAILABILITY OF ABSTRACT 21. ABSTRACT SECURITY CLASSIFICATIONEl UNCLASSIFIED/UNLIMITED 0 SAME AS RPT. 0 DTIC USERS UNCLASSIFIED
22a. NAME OF RESPONSIBLE INDIVIDUAL 22b. TELEPHONE (Include Area Code) 22c. OFFICE SYMBOLJ, W. BAKER (202) 394-2310 R33
DD FORM 1473, 84 MAR 83 APR edition may be used until exhausted. SECURITY CLASSIFICATION OF THIS PAGEAll other editions are obsolete * U.S. OGornment Printing Otflle, S1I-4lIl64
0102-LF-014-6602 UNCLASSIFIEDi
UNCLASSIFTRDSECURITY CI.ASSFIOATION OF THIS PAGE
UNCLASSIFIED
SECURITY CLASSIFICATION OF THIS PAGE
NSWC TR S6-390
FOREWORD
This work presents the results of the safety evaluation performed on theExpendable Sound Velocity Probe. The evaluation was initiated by the ArcticSubmarine Laboratory, Naval Ocean Systems Center, San Diego. The purpose of theevaluation was to obtain approval for internal carriage of the probe unit on boardsubmarines. The safety evaluation performed on the system was conducted inaccordance with NAVSEA Notice 9310 by the Naval Surface Weapons Center, White Oak.
Approv d by:
W.T(.IE ICK, Acting HeadMaterials Division
iii/iv
NSWC TR 86-390
CONTENTS
Chapter Page
INTRODUCTION .............. ...............................
2 EXPERIMENTAL .................... ........................... 3BATTERY TESTING ................... ........................ 3SSXSV SYSTEM TESTING ................ ...................... 4
3 RESULTS AND DISCUSSION ................ ...................... 7BATTERY TESTING ................... ........................ 7SSXSV SYSTEM TESTING ................ ...................... 12
4 CONCLUSIONS ............... ........................... .... 17
DISTRIBUTION .............. ........................... .... (1)
SToo.ualion For'T NTIS GRA&I (
COPY DTIC TABD4 Unannounced
Justification
ByDistribut ion/
Availability CodesAvail and/or
Diet j Speoial
NSWC TR 86-390
ILLUSTRATIONS
Figure Lime
1 SSXSV PROBE/CANISTER CONFIGURATION ............ ................ 22 SSXSV PROBE THERMOCOUPLE PLACEMENT ............ ................ 53 SHORT CIRCUIT OF AN SSXSV BATTERY NOT POTTED IN A PROE. . ..... 74 CONSTANT CURRENT DISCHARGE AND REVERSAL OF AN SSXSV A.LTTERY NOT
POTTED IN A PROBE .................. ....................... 85 RESULTS OF HEATING A PX28L BATTERY ............ ................ 96 lOmA DISCHARGE OF AN SSXSV BATTERY (NOT POTTED IN A PROBE)
TO 50% OF THE ORIGINAL CAPACITY ............. ................ 107 100Wm CHARGE OF A 50% DISCHARGED SSXSV BATTERY
NOT POTTED IN A PROBE ............................. 108 DAY 1 OF A lOmA DI3CHARGE OF AN SSXSV BATTERY (NOT POTTED IN A
PROBE) TO 80% CAPACITY REMOVAL ...... ................. . .... 119 DAY 2 OF A lOmA DISCHARGE OF AN SSXSV BATTERY (NOT POTTED IN A
PROBE) TO 80% CAPACITY REMOVAL ...... ................. .... 1210 CHARGING DATA FOR ONE 80% PREVIOUSLY DISCHARGED
SSXSV BATTERY NOT POTTED IN A PROBE ................. 1211 NORMAL CHARGING DATA OF AN 80% PREVIOUSLY DISCHARGED SSXSV
BATTERY (NOT POTTED IN A PROBE) ....... ................ ...... 1312 DATA FOR THE FIRST 96 MINUTES OF CHARGING A FRESH SSXSV
BATTERY NOT POTTED IN A PROBE ....... ................. ... 1313 SHORT CIRCUIT DATA FOR AN SSXSV BATTERY POTTED IN A PROBE . . .. 1414 CONSTANT CURRENT DISCHARGE AND REVERSAL OF AN SSXSV BATTERY
(POTTED IN THE PROBE) AT THE C/2 RArE .... ............. ...... 1515 RESULTS OF DISCHARGING AN SSXSV BATTERY (POTTED IN PROBE 7) AT
THE C/2 RATE INTO VOLTAGE REVERSAL ..... ............... .... 16
TABLES
Table Page
1 ANALYSIS OF THE OFF-GAS PRODUCTS OF TWO Li/Mnf' 2 BATTERIES .... 16
vi
NSWC TR 86-390
CHAPTER 1
INTRODUCTION
The Expendable Sound Velocity Probe (SSXSV) is manufactured by Sippl.can OceanSystems, Inc. The SSXSV battery is manufactured by Duracell International, Inc.
The SSXSV probe pictured in Figure 1 consists of a small probe and amonitoring lead spool (for transmitting sound data to the submarine), encased in ametal launch canister. The canister is 98cm in length and 7.5cm in diameter. Theportion of the canister which contains the probe and battery is sealed, isolatingthe probe and battery from the outside atmosphere. The battery being used employsa lithium/manganese dioxide (Li.•nO2 ) couple, comprised of three 3-volt (V) calls.The single cells are Duracell DLTN cells. The anode, cathode, and total cellreactions are given by equations 1, 2, and 3, respectively, Two of the DL-N cells
Li - Li+ + e" (1)
Mn Vo .+ Li+ + e - Mn I 1 02 (Li+) (2)
Li + Mn1 Vo2 Mn 11' O2 (Li+) (3)
are connected in series and encased in a metal can by Duracell to make acommercially available PX28L battery. The third cell is then connected in serieswith the PX28L by Sippican to give a nominal battery voltage of 9V. Thecapacity (C) for this battery is rated by the manufacturer at160 milliampere-hours (mAh) at a rate of C/30.
The safety evaluation was performed by the Naval Surface Weapons Center. WhiteOak (NSWC/WC), on the SSXSV system containing the Duracell battery. Preliminaryexperiments were also run on the battery alone. The evaluation was conducted inaccordance with procedures outlined by NAVSEA Notice 9310.
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KSWC TR 86-390
METAL lAUNCH CANISTER CANISTER END CAP
Cl _
SSVPROBE CONNECTINGSPRING END CAP PRESSURE LOCK SPIRING
POTTED Li/MnO2 O-RINGBATTERY MONITORING LEAD SPOOL
MONITORING LEAD COILAND PROBE CHAMBER SEAL
FIGURE 1. SSXSV PROBE/CANISTER CONFIGURATION
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NSWC TR 96-390
CHAPTER 2
EXPERIMENTAL
DLjN cells and PX28L batteries were obtainef by NSWC from DuracellInternational, Inc., for testing. The lot of DLjN cells studied was labeled500084-1 and the lot of PX28L batteries was labeled 500085-1. Seven SSXSV probes(lot label UISSXSV 300648-1), sent to NSWC oy Sippican for testing, weresequentially numbered from 13973 to 13979. Eighteen batteries, independent ofprobe units, and seven batteries potted in probe units were tested. Six SSXSVbatteries were shorted; six SSXSV batteries were discharged at a constant currentand forced into voltage reversal; two PX28L oatteries were heated; three SSXSVbatteries were discharged, followed by charging; and one fresh SSXSV battery wascharged. Batteries in three of the SSXSV probes were shorted and batteries infour of the probes were discharged at a constant current and forced into voltagereversal.
BATTERY TESTING
All batteries except those which were heated to high temperatures, werewrapped with glass tape and FIBERFRAX insulation to simulate the heat retenLion inthe SSXSV system.
Short Circuit TestIng
One DL1 N Li/MnO2 cell was connected in series with one PX28L Li/MnO2 battery(two DL N cells connected in series and encased in a metal can) to produce a 9VSSXSV battery. Six of these batteries were prepared by the staff of NSWC/WO andthen shorted through less than .02 ohm (0). The battery current and voltage weremonitored and the temperatures of the PX28L can (thermocouple no. I) and the DI0jNcan (thermocouple no. 2) were also monitored. 'Five of the batteries were shortedfor approximately two hours and one battery was shorted for 16 hours.
Constant Current Discharge and Reversal Testing
Six three-cell batteries, prepared as before, were discharged through 1120 atthe C/2 rate (80mA rate). When the voltage dropped to 0 volt, the battery wasdriven'150 percent into voltage reversal using an external power supply withcurrent limited to 100 mA and voltage limited to 20V. The voltage and current ofthe batteries were monitored along with the can temperatures of thePX28L (thermocouple no. 1) and the DLjN (thermocouple no. 2).
3
NSWC TR 86-390
High Temperature Testina
Two PX28L batteries were wrapped with TH.MOLYNE BRISKMEAT flexible electricheating tape. These batteries were then heated .(at a rate of 20C/minute) untilthe heating tape failed. The voltage and can temperature of the batteries weremonitored'.
Chargitg Dischared Batteries
*Three SSXSV batteries were discharged and then charged. One of the threeSSXSV batteries was discharged 50 percent of the advertised capacity through a900n resistor at the lOmA rate., The battery was then charged (after incubatingovernight) at the lOO•A rate - voltage being limited to 20V '-to lO0. percent ofthe theoretical capacity. Two of the three SSXSV batteries were discharged80 percent of the manufacturer's rated capacity through a 9000 resistor at thelOmA rate. After -incubating overnight, the batteries were charged at the lOOmArate to 100 percent of the theoretical capacity. TheIvoltage, current, and cantemperatures of 'the PX23L (thermocouple no. 1) and DLjN (thermotouple no. 2) weremonitored.
Charging a Fresh Battery
One fresh SSXSV battery was charged at the 100mA rate for approximately fourhours, The voltage, current, and can temperatures of the PX28L (thermocoupleno. 1) and DL'N (thermocouple no. 2) were monitored.
SSXSV SYSTEM TESTING
All SSXSV batteries are potted Inside a probe using a Jlow stress epoxyencapsulation product (product no. SY6024) manufactured by Anchor Seal EpoxyProducts.
Short Circtit Testing
Three batteries were shorted through less than .020 inside SSXSV probes. Thevoltage, currenc, and two thermocouples were monitored on each probe. For thefirst battery, a thermocouple was placed on the canister and a thermocouple wasplaced just inside the canister (where the voltage leads protruded through aplastic sealing cap). For the next two batteries tested, the placement of thethermocouples was changed. The probes were removed from the canisters and onethermocouple was placed just over the battery on the battery potting - thelocation of the battery was found using a magnet. The second thermocouple wasplaced in the nose hole of the probe. Figure 2 shows the placement of thethermocouples on the probe.
Constant Current Discharge and Reversal Testing
The batteries in the remaining four probes were discharged at the C/2 rate(80mA rate) through 1120 and forced into voltage revtrsal with a power supply,
4
NSWC Th 86-390
The first battery was discharged and forced into voltage reversal with the probebeitig outside the canister so the thermocouples could be easily positioned. Thebattery potting was found to be cracked when the probs was removed from thecanister. Although this condition existed, the nominal voltage of the battery wasnormal (9.8V), and the tesu was conducted. The second probe battery wasdischarged and forced into voltage reversal in the same manner as the first butthe potting was not cracked prior to testing. In order to trap venting gases andtout the durability of the canister, the last two probes wore discharged andforced into voltage revrsal inside the canister. Holes were drilled and tappedin two canisters for a y-Lich NT pipe fitting. An evacuated stainless steelvessel was connected to this fitting to collect venting products. Thermocoupleswere placed on the •,;:tdof the canister ar.dmonitored along with voltage andcurrent.
All voltage, :w.iv-nt, and temperature readings were monitored and storedusing an IMJ( PC.,T . a KEITHLEY data acquisition system. Some important eventswere also recorded on videotapes which are on file at NSWC/WO.
Thermocouple # 2 Thermocouple # I
Hollow Nose Cone
Potted Battery
FIGURE 2. SSXSV PROBE THERlOCOUPLE PLAGEMENT
5/6
NSWC TR 86-390
HIIAPTMR 3
RESULTS AND DISCUSSION
BTTERY TESTING
Short Circuit Testing
Six SSXSV batteries (one DL.N cell in series with one PX28L battery) wereshorted. In less than five minutes voltage readings fell from 9.8 volt to 0 volt.F•g.ure 3 is a representative graph of the short circuit. tests. Note that within'30 minutes the temperature measured on the PX28L battery rose to a peak. On theaverage the peak temperature was 920C. This temperature fell to ambient oveV atime period of about eight hours. The temperature measured on the single DLjNcell, however, remained ambient throughout the test. The SSXSV battery did notexplode, vent, leak electrolyto, or show any signs of disfiguration due toshorting.
7._ -. _ 643
/ \ 4 hPUE.I~S.
1 '4
'IWO
r So 3M
a 36 72 lea• 144
Time (minutes)
FIGUR 3. SHORT CIRCUIT OF AN SSXSV BATTERY NOT POTTED IN A PROBE
7
'4 '-4
NSWC TR 86-390
Constant Current Discharge and Reversal Testing
Si: SSXSV batteries were discharged at a constant current and forced intovoltage reversal with c pnwer supply. The batteries were diszharged at the 8Or•Arate to 0 volt and then additionally driven 150 percent into voltage reversal atthe -ame current. The voltage continued to drop and by the end of the testreached approximately -1OV. During the first 75 minutes of the test, the voltagedropped markedly (on the order of 1OV) and then leveled off for 65 minutes.During the last portion of the test, the voltage again dropped. During thisperiod the current also dropped (Figure 4). The average maximum temperaturerecorded on a forced overdischar e was 57 C. This maximum temperature was againrecorded on the PX28L and the DLjN cell can temperature remained ambient. Likethe batteries that were shorted, the batteries discharged into reversal did not
explode, vent, leak electrolyte, or show any signs of disfiguration.
II III 280
7500 2130~
"Thermocouple #1"1..1 51 '• 14I•140
7 " --. ..........5 ~25 TO$
Thermocouple *2
I 54 1I0 162 216Time (minutes)
FIGURE 4. CONSTANT CURRENT DISCHARGE AND REVERSAL OF AN SSXSVBATTERY NOT POTTED IN A PROBE
High Temperature Testing
Twu PX28L batteries were heated; at temperatures above 2000C, the negative
ends of :-'- batteries vented and severed the heat tapc A few minutes prior to
the batteries venting, the open circuit voltage (OCV) faltered and began to drop.Figure 5 is a representative graph of a high temperature test conducted on a PX28Lbattery. The maximum temperatures recorded were 3500C and 4350C at the momentwhen failure occurred. Each cell in the battery failed at approximately the sametime (differING by less than five seconds). The first cell failure occurred whenthe temperature maximum occurred. There was a small amount of burning (flameslasting less than ten seconds) associated with the failure of each battery.
8
NSWC TR 86-390
......... ............ ................................. IdI't,.A SOB
S375
FIGURE 5. RESULTS OF HEATING A PX28L BATTERY
Charging Discharged Batteries
Three SSXSV batteries were discharged at the l0mA rate and then charged atthe 100mA rate. The first battery was discharged 50 percent. During thedischarge, the temperature on the PX28L and the DL-jN rose less than 50C. During
0 0
cha,:ging, the temperature on the DLyN remained ambient but the temperature of thePX28L rose to 840C. However, there was no explosion, venting, leakage of theelectrolyte, or any signs of disfiguration. Figures 6 and 7 show the dischargeand charging curves for this battery. The next battery was discharged at the 10mArate to remove 80 percent of the capacity. The discharge took place over a periodof two days and the temperatures measured on the PX28L and the DLtN remainedambient. Figures 8 and 9 show the discharge curves for day one and two,respectively. Following discharge, the battery was charged at a current of 100mA.Thirty minutes into the charge, the battery vented. Small flamnes were observedwhich lasted about five seconds. IFrom the beginning of the test, the temperatureon 1the PX28L increased but the DLjN temperature remained at ambient. It was theDL-jN that had ruptured even though its temperature was the one that remained atambient. The temperature on the PX28L peaked at 1080C. The flames associatedwith the rupture burned in the area where the thermocouple was located on thesingle cell. For this reason it was deduced that thermocouple no. 2 was notworking properly, which gave false ambient readings on the DLjN cell. The currentfor this test started at 100mA as planned but unexpectedly increased to 220mA atthe time of and just before the rupture. Figure 10 is a summary of this data.Another SSXSV battery was tested in the same manner to try and reproduce theresults obtained in the previous charging. The results, however, were not thesame; during charging the
9
NSWC TR 86-390
10 _35 -400
9 Thermocouple MI 26.25 -300 r0........ ...... •.......QJ 0
00STHermocc 1* 02 1-
0~-0 -- 475® B
'-4 Q.0100 E-4
0
0 114 228 342 458Time (minutes)
FIGURE 6. 1OmA DISCHARGE OF AN SSXSV 3ATTERY (NOT POTTED IN A PROBE) TO50% OF THE ORIGINAL CAPACITY
20 100 400
THer-mocouple *12
0 5 0410 so 20 -
Time (minutes)
FIGURE 7. i00i CHARGE OF A 50% DISCHARGED SSXSV BATTERY NOT
POTTED IN A PROBE10
lo0
S. . .. . . .. . . l
NSWC TR 86-390
10 -50 129
Vol tage- ~~~~3 . -.90'--'- - " -* .-. *----"-.. . .._ . 37*.5 _ 99
v 5Ther-moccuple 0Al 25 • 64) .... *_t~~~~~~ ..... " ...... "."........... ....... "... . . .. . . .. 4 -
Do --
Thmermocouple &2/24.)
144)0 $4
> 2. .12.5 30
j Cu,-rnt.
____ _ __ __ .0 1.6 S.2 4.8 6.4
Time (hours)
FIGURE 8. DAY I OF A 10mA DISCHARGE OF AN SSXSV BATTERY (NOT POTTED INA PROBE) TO 80% CAPACITY REMOVAL
11s5o 120
fvoltewe ~~. 4.p.5 -0 290
Thermocouplm &I":........... "" ........ a r o . -..............- -2 5 -6
,4jH 4 4)02 -12.5 E`4 3I>, .
,fCurr.n.
6.4 8 9.A 11.2 12.8
Time (hours)
FIGURE 9. DAY 2 OF A 10MA DISCHARGE OF AN SSXSV BATTERY (NOT POTTED INA PROBE) TO 80% CAPACITY REMOVAL
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INSWC TR 86-390
20 ..................................................................................... -15 0 400
74 "4
9 T-4
I, Thermocouplm #1 _75 -2 0E0
"4 •
epr r o en 4P8 rose o aThermhcouplm *2L iz I a I
I 36 72 1213 144
Time (minutes)
FIGURE 10. CHARGING DATA FOR ONE 80% PREVIOUSLY DISCHARGED SSXSVBATTERY NOT POTTED IN A PROBE
temperature of the PX28L rose to 82 0C after 30 minutes and remained elevated. The1temperature on the DLtN remained at ambient. After 30 minutes, the voltage
dropped and the current remained relatively constant throughout the test.Figure 11 summarizes the charging data of this SSXSV battery.
Charging a Fresh Battery
One SSXSV battery was charged at the 100mA rate for four hours. All thepertinent data was recorded within the first 90 minutes of the test, and after96 minutes the graphed data showed no change. Figure 12 shows the first96 minutes of testing for this battery. The charging current was approximately100mA initially. Forty minutes into the test, the power supply voltageautomatically increased in response to a reduction in current caused by anapparent increase in battery impedance. The voltage reached the upper limit ofthe power supgly at 20V. During this time, the temperature on the PX28L hadpeaked at 105 C. When the current had dropped to about 40mA the temperature begandropping. The DL1 N temperature remained ambient and there was no explosion,venting, or leakage of electrolyte. However, both the PX28L and the DL-N showedsigns of swelling.
SSXSV SYSTEM TESTING
Short Circuit Testin.
Three SSXSV batteries, potted in three SSXSV probes, were shorted. Probe 1
(serial no. 13973) was shorted inside the SSXSV canister. The discharge curve
12
NSWC TR 86-390
20 ...... ... .ISO -400
.*1V 15 too"* 0
4v. orm ouple *116
a .... -- •0*-')c . 2- -a La
* * 0 ii-
S38 72 INS 144Time (minutes)
FIGURE 11. NORMAL CHARGING DATA OF AN 80% PREVIOUSLY DISCHARGED SSXSVBATTERY NOT POTTED IN A PROBE
00
20
S15 E-1 -3 04
Curn $4 11I
"TH ummo mpuple $2
I II
* 24 48 72 91Time (minutes)
FIGURE 12. DATA FOR THE FIRST 96 MINUTES OF CHARGING A FRESH SSXSV
BATTERY NOT POTTED IN A PROBE
13
NSWC TR 8G-390
resembled the discharge curves of the SSXSV batteries pLaviously shorted. Thetemperatures monitored, however, were recorded as ambient. The the-mocouples hadbeen placed on the exterior of the canister; for the next two short circuit tests,the batteries (in probes) were tested outside the canister. Temperatures of thebattery potting were monitored on the next two probes. The discharge curves forprobe 2 (serial no. 13974) and probe 3 (serial no. 13975) were similar to thedischarge curve for probe I in all respects except temperature. The averagemaximum temperature recorded on the potting of the two probes was 350 C, about 10Cabove ambient. Figure 13 is a representative graph of shorting SSXSV batteriespotted in probes. During these three tests, there were no ventings, explosions,leakage of electrolyte, or noticeable disfigurations associated with the probes.Dissection of the probes also disclosed that the batteries had not vented,exploded, leaked electrolyte, or become disfigured.
100 -400
.,q-Va 1 Losgo ~
* 5 - CurrenL 40 j 20
2. ThermocoupIu *1 -................................. ..................... *'
%'\gTHarrnccouple M2
a..................... 0 -00 75 I5O 225 300
Time (minutes)
FIGURE 13. SHORT CIRCUIT DATA FOR AN SSXSV BATTERY POTTED IN A PROBE
Constant Current Discharge and Reversal Testing
Probe 4 (serial no. 13976), the first of four probes discharged into voltagereversal, had a crack in the battery potting prior to testing. The OCV of thebattery was measured as 9.82V. Other OCV's for previous batteries tested werebetween 9V and 10V, so it was decided to proceed with the testing of this probebattery. No cause for the cracked potting was evident. The battery followed anormal discharge, reaching 0 volt, and then went into voltage reversal. After 2.5hours of forced overdischarging, there was a venting (indicated by a "pop")accompanied by the tail. piece cracking almost its entire length around the areawhere the potting was previously cracked. Three minutes later another ventingoccurred (also indicated by a "pop"). When the ventings occurred there was anoticeable smell, similar to the odor of ether. This probe was dissected. From
14
NSWC TR 86-390
the arrangement of the cell, the battery, and the position of the crack it was notpossible to say if thermal expansions, venting, or internal heat from either thePX28L or the DLyN caused the cracking. Testing performed on probe 5 (serial no.13977) was similar to that of probe 4. The results were the same. About 2.5hours into voltage reversal a venting occurred. The highest temperature seen foreither probe was 510C at the time of venting. Dissection of probe 5 revealed thatthermal expansions in the DL.jN and the proximity of this cell to the edge of thepotting was the most probable cause of the cracking. Figure 14 is arepresentative graph for discharging an SSXSV battery (potted in a probe) intovoltage reversal.
1s 6- 400
Thermocouple #2
1 agS-5 -300
... . ... ....."
.......... ......... •. ..................... 03O 3-s20 ,4Ji *mr9LMqepl. 00-5 14) . 0
TU
0 62 124 186 248
Time (minutes)
FIGURE 14. FORCED OVERDISCHARGE OF AN SSXSV BATTERY (POTTED IN A PROBE)AT THE C/2 RATE
Probe 6 (serial no. 13978) and probe 7 (serial no. 13979) were dischargedinto voltage reversal within the SSXSV canisters. The canister of probe 6 waspressure tested by filling it with oxygen (02) to 8 psi. After confirming thatthe canister was indeed a sealed environment, it was fitted with a gas collectionvessel. About 2.5 hours into the discharge (the battery was into reversal at thistime) venting ozcurred with a flame exiting the tube around the o-ring seal.However, this test was judged to be invalid as a test of canister durability.Apparently, a greater amount of 02 than normal was trapped inside the canister,causing this reaction. If this were true, the gas sample collected from thiscanister would be expected to contain more 02 than a sample collected from acanister in which the battery vented under normal conditions. Indeed, massspectrometric analysis of off-gas products, performed by the National Bureau ofStandards (project no. 5533462), revealed that this was the case. Probe 7 wasalso tested in the same manner as probe 6, with the exception that 02 was not usedto check canister sealing integrity. Probe 7 did not vent during discharge intovoltage reversal at the 80mA rate, su 1 ampere (A) was Iriven through the batteryby lOOV which caused a mild venting. This allowed a gas sample to be collected.The off-gas products of probe 7 were also analyzed. From Figure 15 it can be
15
NSWC TR 86-390
10 40 120
12.5 Thar-mocouple *2 30 ' 9
0~~~ .........
-20 7--"0 45 90 135 iao
Time (mhiutes)
FIGURE 15, RESULTS OF FORCE OVERDISCHARGING AN SSXSV BATEY(POTEDIN PROBE 7-1 AT THE C/2 RATE
seen that the voltage and current monitored on probe 7 dropped very rapidly unlikeoher discharges into voltage reversal. Te temperatures monitored on probes 6
and 7 were on the outside of the canister which explains their ambient readingsthroughout testing.
Table 1 lists the contents of each gas collection vessel sent to the NationalBureau of Standards. The report received from the Bureau indicated that noharmful or toxic gases were detected. Hydrogen gas (02) was detected in smallquantities and therefore the possibility nf a minor explosion exists. This couldoccur if the probes were exposed Lo temperatures exceeding roughly 2006C.
TABLE . ANALYSIS OF THE OFF-GAS PRODUCTS OF TWO Li/MnO BTTERIES
Composition, mole percentComponent
Serial # 13978 Serial # 13979
H2 4.1 11
CH4 0.5 6.8N2 58 53
02 23 13Ar 0.6 0.8C02 13 7.8CO - -- 6.8
*HC 0.2 1.6
Consists of one or mors hydoearbon constituoents.
16
NSWC TR 86-390
CHAPTER 4
CONCLUSIONS
The Duracell Li/MnO2 DL4N cell and PX28L battery behaved well under 'ibuisivetesting conditions characteristic of NAVSEA Notice 9310. The SSXSV battery madeof one DL•N and one PX28L connected in series was found to be safe for use in theSSXSV probe. The probe configuration in which the DLjN and PX28L are completelypotted does not allow for thermal expansion. Therefore, probes subjected toabusive conditions can be expected to crack. However, cracking does not lead to asafety problem. Using three DLjN cells connected in series with space forexpansions or packing the cells in soft potting, would possibly improve probedurability. Mass spectrometric analysis of off-gas products (produced by batteryabuse) did not detect harmful amounts of toxic gases. Small amounts of H2 foundin the venting products indicates the need to protect canister units fromtemperatures in excess of 200 0C. However, the canister construction is durableenough to contain ventings of the SSXSV battery. Because of the ability of thecanister to totally contain battery ventings, the SSXSV system is acceptable forInternal carriage on a submarine.
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