Training of electrochemist in battery research and collecting electrochemical and thermodynamic dat

Foley, R. T.

Mitchell, G. D.

English

NASA Technical Reports Server

Research into fundamental phenomena associated with spacecraft electrochemical devices - Calorimetry of nickel-cadmium cells Progress report, 1 Jul. - 30 Sep. 1968

Fundamentals of spacecraft electrochemical devices and calorimetry of nickel-cadmium cell

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https://ntrs.nasa.gov/search.jsp?R=19690031558 2020-03-12T04:24:59+00:00Z
TENTH PROgRESS REPORT
FOR
RESEARCH INTO FUNDAMENTAL PHENOMENA ASSOCI &TED WITH SPACECRAFT
ELECTROCHEMICAL DEVICES--CALORIMETRY OF NICKEL-CADMIUM
CELLS
October 1. 1969 - Augw. 31.1969
Contract No. NAS 6--10106
Prepared by
R. T. FOLEY, and G. D. MITCHELL
N(• 9 40947
.^^t••^•i• b seise
J^^
•.	 • iI
•rii^ ii ni r. _ ^ u.ur• •.
f or
_	 .frws
N Y«I
National Aeronautics and Space Administration
Goddard Space Flight Center
Greenbelt, Maryland
The American University
Washington, D. C 20016
r	 _	 _
Tabic of Cvntrnta
J. w -
Abotm-t .......	 .........0.. ...............................	 i
Lira of tit;,urv-a....... .....................................ii
11ot of tuLlc=:' ........................ ....................iii
I Introduc tion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 	 1
I I
	
'scat Trtirwfer In Tienty Afire- !lour......... 0 0 . 0 .... • 2
	
Ni -cd (vi. ...........................................	 2
A.	 Gdr+c ription of Cell .........................	 2
B e	 Experimental.. .............................. 	 2
C.	 Coto1urIonts ................................. 	 6
III	 Stutir;,!cul F:aluation of : ,ito ....................... 10
A.	 Accumptionn ................................. 10
Be vtat atical Trestasent .. .... . . . . ... . . . . 0 0 0 0 . . 10
C.	 Corw1usIonu ................................. 15
IVHeferencee ..................................•........ 18
rAX.TRWT
The objectivra of thin project are to train elvetrc — itrmletc In th-
area of tattery rctfrarch and to collet clve tr©ehvAi%al hrxl the:akAs;r►^+a^.:
auto of value • to proferta bcirT eonducitJ et tl ►c OKA ,InN 31aze F11C t
Center. nw apecirle exprrico-ntal work deals wit), the calorir_ctn-,; of NI-C-1
crllr.
In the final rvportt.%C p-riod th— work vmzs drsi t-n-A to ung -t er queet!c:;a
denling writ?,	 h,•st trnnafcr in Ow V ampert-hcx►r call an ►d the preciaior+ cf
tiu• date► pr* • vl"ly reported.
fxpvr• irow ntr with r► nickel-cadmium cell opecially febricated .:4th ar.
interr ►ul ralibran . icn: heater indicated n higher signal (100-150 m y/sutt) tu'
a lonCf r rusponsr Liza► (30-50 minute n) than prr►vioue experim-nts -with e
reeletanev wire hater mounted under tlu.• cell	 in tl ►v calorimeter.
M. d a tx, on the G ampc ,• rte -hour cell  and t ?x.• 0 ump, re - hour cell
were evalunte*1 stutivtically. It was eatabliched thc ► t the data frcm tht
20 ampere -hour cell has g confidence level of 89% and a 90.5ii pnbabilit'-
that each w!nvurvment will be between	 f2	 --tundard error. In an cxperizent
In which the mean heat ryas -1 . 035 watts the standard error xac 0.068 %attn.
i
atAnt of Fleurra
der
rivirt- 1.	 Sket-Ch of aPrI l ici l r ' ll with internal
citilbration hqat4•r
r I LVU re	 FIC/W mte of oil th^nigh calorlw-ter
pp lv #+.nt pump atroke
-0
rLira of T4b leo
Page
Tubir l . Waaurrirv-nts on volu:c of oil flow varv,4o
pk t1> a t rvkr	 r*% tv .
Table- :. rive rete Qtw thertal rcvfrxL.r at aattitw 7
of	 0" .
Tat,1c• ;. now rate and thcriml rocporwe at a setting 7
of	 1/4".
Table 4. flc;w rate arA t1m m l re-pone at a settIrw 7
of	 1/r".
Table i. Relationship between flow rate and thermal d
reapontiv at	 11b" :tatting.
Table 6. Relatiorvthip betwr:nn flor sto and theoml 8
rraponre at
	 1/4" aettlu .
Treble 7. Selected datri fm= 25! tleopth of discharge 11
experimenta on trio 6 wnpore-hour nicke3l-
cadmitmn Call.
Table 8. Selected data from 25% depth of discharge 12
experim—ntc on the 20 ampere-hour nlckel-
eadmIum Boll.
Table 9. Calculation of
	
"t"	 for four pointe. 14
Table 10. Standard Error of the Averages for the 6 16
ampere-hour data
Table 11. Standard Errors of the Averages for thn 17
20 ampere-hour data.
W
	
iii
w -	 n
AP
Ikacareh into rWr1wro-s.tal Ftw-ry ,,-r^ Aaa4,<I etcd
with lfpaceeraft Clretrue-healval D&vtc„a--Calorimw%ry
of Nickel-Cn4nium Cr 1 la
I. I UTMCUUCT I CM
Ttw objec t i v--a of thi a vro3Qs' t o r”
1) to t m 1n rloe tm-ht-mats in th- , an-o of batte ry rra vo rch an
2) to collect	 data of Yalu, to pro V'l-- o ts being
conducted at thr Goddard ;ye<• r Flight Center.
Uuri nC t h 1 v f i nu l rvportirW pe r1 od work ,raw pe rflum-rd to u ne ere r two
yucntiow. T?r• firut dealt	 with ho nt transfer in and out of the 20 aspert-
tour nickel -cadmiw. cell. Wanum.mento werr mvie on it specially eonutr.::^:t.
cell equipped with an intortwl calibratl^i ► hcatrr and thrrmocouple.
M arcund queattun dealt with the preetnion ► of th- ?r at data obtalr-
in previous expnr-Imentia on tho , nickel-cadaitam ce lls. Reprec entotive datt
twos a 6 ampere - tour and a 20 afire -hour cell wore;, subjected to t1w "3tudE:.:z"
t test and an evaluation of the sUmdaW error.
1
M }{+-a' Transfer irz Tteunty Axpera •htur Ni-Cd Cull
A. IJOaor• lpticui cif Cnll
In order to ntudy the mar:rl-r in whloh N-at is trafisfarred uut of a
orate•-re -hour :tickal-c isdm mum call uxc}arlontitr were `*rfvrowd with ti
npacia1 orll aonAtruated aith an 1ntvt.A1 rvoistaswe heater. This cell
wa:! a Gulton lndur triov -all  type Y0-20 ti. NI-Cl con e• fabrics• to ;l with
a strip of raa1stance alloy and an 1run--owictantan uwn&Qcvuple. A
rketch r.)f thin cell is given in flgure 1. The resistance akauurwd fr.em
Point a to b Ic 0.56 O atW the roviatance of the Internal heater '.a
upproximute-YIj U.8 G. it is cell with the excepticn of the heau•r and
the rmoc oup le in av auxx- d to b•? similar  to the 20 &rap-. r e - h mr cell upon
which preeioju experimentu wrrc perforeed.
B. L x pe rime nta 1
Following the reauv%mtly of Ube calorimeter a set of calibration
exparime+nt.0 were performed to Jetermine the volume of oil pumped at given
flow rates A cerieu of mraeuivrorntS were made in which oil wav pumped
through the calorimeter  at different stroke rates of a roe to ring pump and
samples of oil were collected over a r1rin time interval. The linear
re la t i onsh tp between e t robe rote (thee vetting on the pump) and the
volume of oil is shcuia in table 1 and figure 2. This eonverolon can be
used with they data given below.
The thermal reepcs ►ae of the cell with the internal heater was
measured at a series of different flaw rates and thermopile pocitionu.
In each cave a current of 1.10 ampereo, equivalent to an input of 1.10 watts
* Gulton Drawing No. 552-W4750, NU 20 HS Cell Assembly With Heater and
The rmocuuple .
2
Turs^^OCOUPLE
conttcnton )
INTE. 4AL
HEAZER
approx.
0.80%
Figure 1. Sketch of special cell with internal calibration heater
3
3
I
TAhU I. YNOur--awmto on Vahow of (41 ►loo Yernum 11rap 3trok., wit*
I
M11Mr. kAT2 ti )
50
50
50
40
40
40
50
50
30
20
20
10
YOUM(al ) TIW (owe)
Jb'0 10
450 10
450 10
35 10
375 10
5" 10
J90 10
290 10
290 10
170 10
170 10
170 10
,.
4
n
1r
i
r
r
•
a
w
O
WO
w9
O
co
NO
w
2
 
P
 X ( ulw
l**) 31da *01.4
Nina
r
r9" api► Iiatl ta, tM hr4 t 117r SW tt, g ai I 11-eA t rvapctwe won swosure4 <_yYer a W.riod
of tU* until a ctcady # tat* we- achieve,. In taties ^, 5, arrl 4 moart4ru a ws
a m e 1vQ:, f •^r u&rec them,.p:io pow iticw , 0-, 1/4 n , arxt 1 /^ 0 re #M oti v'C ly
Ttav vc latter figure # la.! ioa to tha " i t i uni:o; ,a ttw ttw nwp i le with
ree`=-at t tta -e xit r -rt of ttw oalurixv- ter, r.	 1/4" indlcatvo vat t1w
end of the themvi to sea lc .oatwd 1 /4 inch frm tho exit port.
Inepectlart fit table 2--, inaicotr a that •.:a aignal we.,. hi jtar ttat:
that t.tze nred
 
in calibration	 sherain a taster wir y one located
bencatit the cell i:. the calorl,awter. Tablas 5 and G acs taken frtr. ttwr
Eighth Prvgre s.,v R*;K rt ( 1) for cc ;Anson. In tl.ix previv" series of
experizut is a typical restar.ze war 40 ry /watt. T?e oalorionter napcewo
to the into rria 1 heater war 100-VA ov /watt . On the otbv r hand thw
reaponae :isms in the latter case is ccinsiderably laWer. A typical
response in 5 minutes war 10-25$ of the signal a:hiev94 at the plateau
(af ce r 50 - 50 minutes) . There is no obvi ous axplanstion to ttw non- linear
bolavior a.axisted with the positioning of tht, theMopile, i.e. the
•	 restK"s q t 1 /4" is not half way between that of O" and 1/2" . At this time
It can on',y be assigned to the pattern of oil flow within ttw calorimeter.
C. Conclusions
The purpose in testing a c sll with at. internal !seater was to provide
a method of calibratiun that -more closely reaerabled that or the actual
operating cell. It in obvious that the Internal heater operates more
efficiently in the sense of sensing all of the heal put in. However,
the internal heater mutt heat the entire oell before a plateau is reached
iu the - ignal and in this sense does not reproduce the mechanism as it
oeeurc lu the operating cell. In the oell as it is supplying electrioal
6
Sir- ,na 1 my
lOp.5
lay
145
162.5
St roke
60
50
40
30
Maporwe (' in c rt..
20.5
25.8
25.8
22.3
r	 ,
TMU ;'. flu• ratt and thermal mopm ar at a awtting of (r (30 aiO
3117101 ( MV)	 a tmks-	 krnmwf, C' F - ! ,1
8o	 65	 12.5
	
97. 0; 	 60	 15.6
	
M .5	 50	 1 5.2
	
175.0	 40	 1L.3
	
200.0	 50	 15.0
TAMP, 5. flow rate rind thermal r+nNnur at a settirw of l /»" (40-50 `In)
SIMui1 (nv) 't rake, 5 ':•.
35 65 1 ^^
92.5 60 13.5
80 50 12.5
157.5 40 17
157 . 5 30 20.5
TAJIU 14. Flow rote wW thermal r:aponne at tj setting of 112" (near SG min)
7
n
TAtsl.t 5 . ko is t tuemrA i p tart wert ► f 1 ow rate and thervA 1 rra p cmo at 1 /8"
rKtti fw
 (1.13 vm tt i npu t)
.^E'!L4:	 ^'r►Y^ st rok• r- jonvo-
-
(^ in	 min)
67 -8 25 62
35 40 69
5 1 45 79
28 5 o 79
27.G g
^
8 3
19 65 84
TABLE 6. Rclatiowhip botmen flow rate and thom.&I respo.re at 1/'."
setting (1.11 era t t Input)
SiE*nn 2	 (mv St rvke Respcmac (5 in
	
min)
41 20 15.6
36 25 75.3
31 30 TT.4
27 40 81.5
3280 80. o40
S 79.0
42 55 81.0
41 57-5 83.0
39 60 89.0
33 65 85.0
anrrry ttu+ heat is Crtwmited at the electrodes and heat 1a only invOlvtd
after Ow eleetrieftIly tenrratrd tvFat too auyplfed the heat euff1clont to
weet the tK•at capacity mquir-mcnte of the cell matoriala. The actin point
here- to that t• , arr interrotrd in the heat as it apjw-ara at ttu, ce11 wm11.
TU, rr npvwe t 1xie IWtcatt-d in t4t,1ra 2-4 can not tw tivd to tt* DattrrS'
rycltr4- witt"t takinj into account the- twat ou;Aeity of the, vote: ial
art t hi n t hr cell
r
I. statiatinal Eye luatlun of tant.n
A. Asseweptivne
Any rvalust1t4i or interpivtatiun of the oalurirv-tric date vn tte
project auts t be rem t rit tefi by Lire precis ion and accuracy of Ot"
vxp,.rlm;,ntn. The only previoto att••mpt to ertabliesh the interrnl
cutwiatoncy of tho data sacs that given ii& the First Prvgreas Ralurt
(2) wtwro in a number of to Jon of data wery reporteJ aid ttk.•
 in-
spectivu of which indicated a Cow reproducibility of the experlw_,nta.
awouurvewtit::. bcosume of thin indication, of reproducibility the data
for the :six ampere-hour cell is taken an standa" or reforrnee rata.
In order to make a com;ro ri sun ba twven the 6 amps re-hour cell an„ the
L'U ampone-hcru cell it was ascumc:d that there were no factory 1nvolv*.:
in Uw manufacture of either type of ee11 t.%at affectto thn reprvducit:::-.y
of uperstiun of cells in a comparative uenxe.
B. Statictical Treatment
The data shown in tables 7 and 8 were `en from previously repo:el
e xpe r ime n to on tin 6 ampere-hour and 20 ampere-hour cells respectively
(2,5). They were both conducted at 2516 depth of discharge and 110r
rate of charge w d zvpmeent typical runs. In these teblas "x" is the
heat aboorbed in watts; the subscript indicates a particular cycle.
The eva qua t ion of the data for the two cells was begun by using 1--.1
"Student's" t test. The application of the t test to the data shown :n
table 7 and 8 allows  a statement to be made o an ce rn ing tht d i f fe re nc r r
between the 6 ampere-hour cell and the 20 ampere-hour cell. By the
calculation of the values for t it can be concluded that the probability
r
10
rTAMS 7 •	 e Lo too 4e ti f rL= 25*  dep th of dischu eor
ospurismitto on tlw 6	 re-hour niokol-o+WaNm *oil.
(Taken f rule m f e- tv n e a ?, )
pI:% W IAltc:^
T im" X1 so X3 X 4 xo xe
10 -o.-',6 -0.66 -0.66 -0.66 -0.66 -0.66
20 -0.65 -0. "' -0.64 -0.65 -0.62 -0.65
50 -0.58 -0	 , -o-6o -0.58 -0.58 -0.59
CILAWZ
Tim, X1 is X3 xo xe xe
10 -0.1 !) -0.14 -0.14 -0.14 -0.15 -0.10
20 +0.04 +o .o6 +0.06 *0.014 •0.05 +O .U6
}o +0.10 +0.10 +0.10 +0.08 •0.10 +0.11
150 •0.09 •0.11 +0.09 +0.10 •0.11 •0.10
50 +0.05 +o .06 +0.06 +O .o4 +o .o6 +0.02
11
12
W11! 0.:a1ectod data fro *i * :icy pth of d1achargc Mxp+rL manta on
ttw 20 expore-h&-ur n1aiw1-Oottslus *all.
(Tejon f" rvfC r"rave 5)
xx v 13 X4 xg xo
-1.04 -0.95 -1.10 -0.95 -1.04
-1.2-1 -122 -1.50 -1.50 -1.55 -1.25
-1.25 -1.25 -1.35 -1.55 -1.57 -1.27
GL WARM.
T lei
10
20
30
Y 1 X* X3 4 IS xe
-0.7) -0.69 -0.77 -0.80 -0.95 -0.79
-0.27 -0.25 -0.52 -0.29 -.0-55 -0.29
-0.05 0.00 -0.07 -0.05 -0.07 -0.05
+0.07 +0.07 +0.05 +0.01 +0.07 +0.07
+0.05 +0.01 +0.01 0.00 +0.01 0.00
miWAY.
TLw
10
20
50
4u
50
I0
of bsit,er ervog in sayine that a letinite t1rrtre n:n exl«tz between tt.e 6
amq•e re-h4mr oe l l and the 20 ar4c re -N ur call each of the t is - r tested in
(( 0.01. Tab le !) st ars the pmtabi L1 ty taken for four points ^f thr-o to tx of
data, 1.0. UUVV- ayl loa Ub" lr 1
 A, d, meld G sue Otr Ce i vr ly. The ro latIon
us-ad in calculating the va 1ue for t is the cmr umv i for the co"rissw. of
unpai rpd va riab lie r
.x
z
whir r• in
i l l • individual neasurrment f ► -Am 20 amt.-re-hour data
xe i . ind ividual mean u re taint f ram 6 ampere-hour data
icy . mean of the 20 ampere-hour me asummants
icy . mean of the 6 amp re-hour measurements
N i & numt,er of meauuremnnts of x l variables
Mg . numbe r
 
of measur vents of xe variables
The cuq*ris()n of t (calculated) with t (tabulated) shows it be greater in
every cane. This indicates that a probability of (( 0.01 that differencen
between the two cells was by chance only.
The second test performed on the data was a yeas ure of the standard
error (S.E.) of the averages. for the number of meacumnwnts taken, the
data exhibited a 80 confidence level for 2 S.L. The probability that each
measurement will fall between _ 2 S .E . is 90.5%. (5) . Table 10 gives the
standard errc ,r calculations for the six seta of data taken from table 7 for
the 6 ampere -hour cell and table 11 for the 20 ampere-hour . ;ell ( table 8 data) .
13
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P4
P4
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.0
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K
^
^
7
N
%0
^
' Q
q
g
'.
4
4
4
4
>^•4 4 4 4
^ 4 4q°
In ttwrc tablee the varWwes w» calaulato4 as
^'	 s0.1	
X, X•
and the s Uui,.Urd a rrur
The prrrciaicn of each maosum-r.,ent or this typo Is rvprcnentes t,y 9-hp
s tandard a rrur given In the 16 th column of ttw tables. The U to for -a.* 6
W%-re-hour call hat; tw- n ausslme4 to to ttw a tanoa rd or re f c rence da ta ana
thug the ntandard errury gi yrn in table 10 i v considemd to be ttw
experiawntal error for a measurement of this type.
C. Cunc luv ionu
In comparing Ube 20 ampere-hour dat4 the re are two uignificant fa: tare,
ttw first, a larger cell was tasted and secondly, a large r calorimeter sar used.
The calculations frum table 9 indicate that there is an ittwrent d if f -Mice
be tween tte 6 and 20 ampere-hour ce1lm. There is no indication that ',to
precision involved in using Uw lamer calc ►rimeter w ill be lose: vtan that with
the esma lle r . The significant  conclusion drawn f rum this study Is that the
data from the p re v 1 ouc reports cos the oa for imr t ry of the 20 ampere -hau r n i c loo 1-
cadmium cell has a confidence level of 69* and a 90.5$ probability that •ach
masurrment sill be betmmn . 2 standard error.
15
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7ka re re two a
1. N. T. Foley wry! G. D. YitaMil. "h- &.aarch litt y vWt Iawntal i'rxtrxx r,a
Assmtatcd with °p4adav%rt floatrcct oaWsl tpvlccs - CaLorf vtry =f Wl.iwl-
Cadalm	 fignth Nrv-grorm P -;,rt ut) Crmtreat W -101U,, April 1,
Jk.tw 30, 1	 .
2. W. N. lebo:er and N. T. ►nisy, tirvt PrVrear R"Port, va Cantmot NA:;
WW.,,, Jar:uary 1, l td  - Z;ert4mt)or 50, lcflr6.
5. P. T. Foley,	 V. Ul teha l l ate! G. N. Rubo rto , ;:a venth Prue rear Hepurt
on Ccsttmct RA3 5-10105, JwitAry 1, l 41i - Uurvh 51, l(0.
4. K. L. Crum, ";tatlatics Mhty al", table 50 i'fj
. 
25, Duver Publieativra,
Nv* York, N.Y.  (191)01.
5. M. L'xakla 1, "W ttvx4s of Curre latlun vW Rr i:msslm ArAlyc la" ;,g. 25,
figu v 2.1, JuWi rilvy#:aw, tic. N.. Yv:lc, N.Y. (1965).
18


Research into fundamental phenomena associated with spacecraft - Electrochemical devices and calorimetry of nickel-cadmium cells  Progress report, 1 Oct. 1968 - 31 Aug. 1969

Electrochemistry and thermodynamics of nickel cadmium batterie

Research into fundamental phenomena associated with spacecraft electrochemical devices - Calorimetry of nickel-cadmium cells Progress report, 1 Jul. - 30 Sep. 1967

Research into fundamental phenomena associated with spacecraft electrochemical devices - Calorimetry of nickel-cadmium cells Progress report, 1 Jul. - 30 Sep. 1968

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NASA Technical Reports Server

NASA Technical Reports Server