llbers for 1exLlle8ased LlecLrlcal Lnergy SLorage

ro[ecL M06Cl07
Leader SLephen L Creager / LlecLrochemlsLry and power sources
Members hll 8rown / llber Sclence ulck Cregory (Cld uomlnlon unlverslLy) /
ConducLlve olymers
CCAL S1A1LMLn1
1he goal of Lhls research ls Lo fabrlcaLe and LesL flberbased capaclLors sulLable for
elecLrlcal energy sLorage ln mulLlfuncLlonal LexLlle producLs CapaclLors wlll conslsL of a
conducLlve flber core coaLed wlLh a Lhlnfllm ceramlc or polymer dlelecLrlc whlch ls
coaLed wlLh a secondary conducLlve layer
A8S18AC1
1hls research wlll demonsLraLe feaslblllLy for manufacLurlng flberbased ceramlc
capaclLors sulLable for elecLrlcal energy sLorage wlLhln mulLlfuncLlonal LexLlle producLs
CapaclLlve energy sLorage ls well maLched Lo appllcaLlons requlrlng hlgh speclflc power
long cycle llfe and hlgh rellablllLy We are uslng a slmple chemlcal scheme for
preparlng flberbased capaclLors by coaLlng elecLrlcallyconducLlve flbers wlLh an
ulLraLhln layer of a conformal plnholefree dlelecLrlc fllm followed by coaLlng wlLh a
second elecLrlcallyconducLlve layer Lo creaLe Lhe capaclLor AppllcaLlon of a poLenLlal
dlfference beLween Lhe Lwo conducLors creaLes an elecLrlc fleld across Lhe dlelecLrlc fllm
whlch accompllshes capaclLlve energy sLorage Lnergy sLorage ln capaclLors scales wlLh
Lhe square of Lhe elecLrlc fleld across Lhe dlelecLrlc Lherefore ulLraLhln dlelecLrlc fllms LhaL
are plnholefree and reslsL dlelecLrlc breakdown when large elecLrlc flelds are applled
across Lhem are deslred ln one approach fllms of approprlaLe hlgh ceramlcs lncludlng
LanLalum LlLanlum lanLhanum and hafnlum oxldes wlll be formed on elecLrlcallyconducLlve flbers of
sulLable maLerlals lncludlng alumlnum carbon and elecLronlcally
conducLlve polymers such as polyanlllne ln a second approach ulLraLhln polymer
dlelecLrlc fllms wlll be formed on Lhe flbers by a comblnaLlon of splnnlng and layerbylayer
polyelecLrolyLe deposlLlon ln boLh cases Lhe resulLlng dlelecLrlcfllmcoaLed flbers
are subsequenLly coaLed wlLh a second elecLrlcally conducLlve ouLer layer Lo creaLe Lhe
deslred capaclLor flber rospecLs for lnLegraLlon of Lhe resulLlng flbers lnLo flber bundles
yarns and woven fabrlcs Lo be used ln creaLlng mulLlfuncLlonal energysLorlng LexLlle
producLs are belng explored n1C ro[ecL M06CL07
age 2 of 9
naLlonal 1exLlle CenLer Annual 8eporL november 2006
ln18CuuC1lCn
CapaclLors are useful energy sLorage devlces ln appllcaLlons where hlgh speclflc power
long cycle llfe and hlgh rellablllLy are especlally lmporLanL ln conLrasL wlLh sLorage
baLLerles Lhere are no chargeLransfer or chemlcal reacLlons ln a capaclLor only charge
separaLlon across a dlelecLrlc maLerlal CapaclLors are Lherefore noL sub[ecL Lo Lhe klneLlc
boLLlenecks and fallurecauslng dlmenslonal changes LhaL are commonplace ln sLorage
baLLerles SolldsLaLe ceramlc capaclLors are especlally deslrable due Lo Lhelr fasL response
Llme eg subsecond vs Lens Lo hundreds of seconds relaLlve Lo redox and
elecLrochemlcal doublelayer capaclLors Also solldsLaLe capaclLors conLaln no llquld
elecLrolyLe LhaL could poLenLlally leak ouL and cause devlce fallure 1hls laLLer polnL ls
especlally lmporLanL ln mulLlfuncLlonal maLerlals for whlch such a fallure could
compromlse oLher maLerlals properLles relaLed Lo funcLlon
MaLerlals properLles needed Lo achleve hlgh speclflc capaclLance ln a solldsLaLe capaclLor
lnclude Lhe followlng a Lhln plnholefree layer of a maLerlal wlLh a hlgh dlelecLrlc
consLanL whlch can supporL a hlgh degree of charge separaLlon ln a large elecLrlc fleld
wlLhouL falllng eg by dlelecLrlc breakdown elecLron emlsslon or charge moLlon a large
surface area wlLhln Lhe capaclLor volume and low overall mass MosL presenL solldsLaLe
capaclLors achleve Lhese properLles uslng polycrysLalllne lnorganlc ceramlc maLerlals
arranged ln layers on Lhe order of a few mlcromeLers Lhlck ln a planar sLacked geomeLry
wlLh alLernaLlng ceramlc and currenLcollecLor elecLrode layers 1hls approach ls well
sulLed for fabrlcaLlng capaclLors for mlcroelecLronlc clrculLs and for creaLlng dlscreLe
llber coaLlng
wlLh a Lhln
dlelecLrlc fllm by
conLlnuous solgel coaLlng
CvercoaLlng
Lhe dlelecLrlc
fllm wlLh a
second
conducLlve
layer
llgure 1 lllusLraLlon of Lhe fabrlcaLlon sLeps LhaL wlll be used Lo creaLe flberbased solldsLaLe
capaclLors llber coaLlng wlll be accompllshed by sLandard meLhods whlch are fully amenable Lo
conLlnuous rollbased hlghvolume manufacLurlng n1C ro[ecL M06CL07
age 3 of 9
naLlonal 1exLlle CenLer Annual 8eporL november 2006
clrculL elemenLs buL Lhe resulLlng capaclLors do noL scale well for power capaclLor
appllcaLlons and Lhey are noL well sulLed for capaclLor fabrlcaLlon ln complex form
facLors eg ln LexLlle producLs LhaL are usually requlred ln mulLlfuncLlonal maLerlals
Many areas of LexLlles usage are also areas where lnLegraLed mlcroelecLronlc funcLlonallLy
ls becomlng common and lnLegraLlon of mlcroelecLronlc clrculLry and funcLlon lnLo
LexLlles ls ofLen deslrable buL ls noL easlly accompllshed 1here exlsLs a crlLlcal need for
elecLrlcal energy sLorage maLerlals LhaL can be easlly lnLegraLed lnLo LexLlles Lo faclllLaLe
lnLegraLlon of mlcroelecLronlc funcLlonallLy lnLo LexLlle producLs
Approach
We are uslng an enLlrely new approach Lo capaclLor fabrlcaLlon based upon Lhe use of
elecLrlcally conducLlve flbers as currenLcollecLor elecLrodes llgure 1 lllusLraLes our
approach We sLarL wlLh Lhln conducLlve flbers perhaps of carbon or a base meLal such as
alumlnum boLh of whlch are commerclally avallable AlLernaLlvely flbers made from an
elecLrlcally conducLlve polymer such as polyanlllne whlch one Leam member has
prevlously prepared ln a solld flber formaL could be used1 We wlll use solgel
Lechnlques Lo coaL Lhe flber wlLh an ulLraLhln (few Lens of nanomeLers) fllm of a hlgh
ceramlc maLerlal whlch wlll serve as Lhe acLlve dlelecLrlc maLerlal ln Lhe capaclLor Solgel Lechnlques are
well sulLed Lo maklng fllms LhaL are very Lhln conformal Lo subsLraLes
havlng a complex shape and plnholefree 1anLalum LlLanlum lanLhanum and hafnlum
oxldes are of parLlcular lnLeresL2 due Lo Lhelr favorable comblnaLlon of hlgh
permlLLlvlLy hlgh dlelecLrlc sLrengLh and low leakage currenL and Lhey wlll be Lhe focus
of our work 8ecenL work from kunlLake and coworkers ln !apan lnvolves developmenL
of solgel Lechnlques for creaLlng Lhln plnholefree fllms of Lhese oxldes on slllcon
surfaces for evenLual use ln fabrlcaLlng lnLegraLed clrculL capaclLors3 4 We wlll adapL
Lhese Lechnlques for our work wlLh flber subsLraLes AlLernaLe approaches based on
aLomlc layer deposlLlon (ALu) have been successfully used Lo prepare ulLraLhln ceramlc
fllms on subsLraLes wlLh a complex form facLor3 buL we belleve LhaL Lhe solgel
approach wlll be superlor for hlghvolume flber processlng and Lhls ls Lhe approach we
wlll pursue
lollowlng Lhls sLep a second coaLlng ls applled Lhls Llme of a maLerlal whlch wlll produce
a conducLlve ouLer coaLlng whlch comprlses Lhe second elecLrode ln Lhe flberbased
capaclLor CpLlons for preparlng Lhls ouLer conducLlve coaLlng lnclude Lhe followlng
polymerbased maLerlals whlch could be carbonlzed ln a followlng Lhermal sLep Lo
produce conducLlve graphlLlc carbon composlLe maLerlals conLalnlng meLalllc conducLlve
addlLlves (eg gold nanoparLlcle suspenslons) elecLroless plaLlng of meLals such as nlckel
or copper coupled wlLh lowLemperaLure flrlng and flber coaLlng uslng elecLrlcally
conducLlve organlc polymers such as polyanlllne and polyLhlophene and derlvaLlves Cne
of Lhe Leam members (Cregory) has experlence uslng elecLronlcally conducLlve polymers
as elecLrodes ln solldsLaLe capaclLors ln convenLlonal (planar) formaLs and LhaL
experlence wlll be well maLched Lo Lhe presenL pro[ecL 1he end resulL of Lhese sLeps wlll
be producLlon of a coreshellclad flbrous maLerlal LhaL can funcLlon as solldsLaLe
capaclLor capable of elecLrlcal energy sLorage lndlvldual flbers could subsequenLly be
lnLegraLed lnLo bundles uslng elecLrlcally conducLlve blnders wlLh a varleLy of Lechnlques n1C ro[ecL
M06CL07
age 4 of 9
naLlonal 1exLlle CenLer Annual 8eporL november 2006
common ln LexLlle processlng and Lhe resulLlng bundles would also funcLlon as solldsLaLe
capaclLors and could be used Lo lnLegraLe elecLrlcal energy sLorage funcLlonallLy lnLo
LexLlle producLs
A flber bundle formaL ls aLLracLlve for power capaclLors because lL offers a hlgh surfaceLovolume raLlo
wlLhln Lhe flber bundle whlch comprlses Lhe capaclLor volume A hlgh
surfaceLovolume raLlo allows for use of Lhln ceramlc layers across whlch a hlgh elecLrlc
fleld may be easlly applled uslng modesL absoluLe volLages Lnergy sLorage ln a capaclLor
ls proporLlonal Lo Lhe square of elecLrlc fleld Lherefore lL ls lmporLanL Lo use hlgh flelds
achleved by applylng modesL volLages across very Lhln fllms Lo achleve hlgh energy
sLorage denslLles 1hln ceramlc fllms are easlly applled Lo many solld subsLraLes Lo make
sandwlchsLyle capaclLors buL Lhe overall volume fracLlon of ceramlc maLerlal ln Lhls
conflguraLlon ls ofLen low so Lhe volume and massnormallzed energy and power
denslLles are also low llber bundles are Lhus an aLLracLlve conflguraLlon for achlevlng
hlgh power and energy denslLy LhaL happens also Lo be hlghly compaLlble wlLh LexLlle
producLs Some llmlLed modellng work has been pursued on flberbased solldsLaLe
capaclLors whlch suggesLs LhaL Lhey should have favorable properLles6 buL Lo our
knowledge no experlmenLal work has yeL been reporLed llberbased elecLrodes are
wldely used ln elecLrochemlcal doublelayer capaclLors buL LhaL formaL would hardly be
approprlaLe for a LexLlle maLerlal glven Lhe requlremenL for a llquld elecLrolyLe and a
sealed cell 1hus Lhe comblnaLlon of solldsLaLe ceramlc capaclLors ln a flber bundle
formaL ls unexplored LerrlLory
1he pro[ecL Leam conslsLs of Creager an elecLrochemlsL wlLh experlence ln
elecLrochemlcal power sources79 and elecLrode surface modlflcaLlon10 11 8rown a
polymer flber sclenLlsL wlLh experlence ln flber splnnlng and processlng lncludlng
elecLronlcally conducLlve polymers1 and Cregory a chemlsL / maLerlals sclenLlsL wlLh
experlence ln elecLronlcally conducLlve polymer synLhesls and processlng lncludlng ln
flber formaLs12 1he comblned experLlse of Lhls Leam ls ldeally and unlquely well
sulLed Lo Lhe pro[ecL ob[ecLlve of fabrlcaLlng and LesLlng of capaclLors based on Lhln fllms
of ceramlcs meLals and elecLronlcally conducLlve polymers ln a flberbased formaL
rogress from May 1sL 2006 SepLember 2006
1he formal pro[ecL sLarL daLe was May 1 2006 however we dld noL have any sLudenLs or
posLdocs avallable Lo sLarL work on Lhe pro[ecL Lhen Lo Lhe pracLlcal sLarL daLe when
pro[ecL work acLually began was noL unLll Lhe sLarL of fall semesLer ln AugusL 2006 So
we have llLLle ln Lhe way of concreLe resulLs Lo supporL 1here are now Lwo Clemson
graduaLe sLudenLs workers assoclaLed wlLh Lhe pro[ecL one a flsLyear hu sLudenL ln
maLerlals sclence and englneerlng worklng under Lhe [olnL dlrecLlon of hll 8rown and
SLeve Creager and Lhe oLher a fourLhyear hu sLudenL ln chemlsLry worklng under Lhe
dlrecLlon of SLeve Creager 1hese sLudenLs are sLarLlng laboraLory work on Lhe pro[ecL ln
fall 2006
1he followlng paragraphs provlde some deLalls on our plans for pro[ecL work Lhls comlng
fall ln some cases Lhls maLerlal elaboraLes on Lhe pro[ecL proposal and ln oLher cases new n1C ro[ecL
M06CL07
age 3 of 9
naLlonal 1exLlle CenLer Annual 8eporL november 2006
ldeas are descrlbed All of Lhe pro[ecL work wlll sLlll remaln focused on Lhe pro[ecL goal
of developlng flberbased LexLlle capaclLors
ConducLlve flber subsLraLes
We plan prellmlnary sLudles uslng
alumlnum meLal wlres as conducLlve
flber subsLraLes Alumlnum ls avallable
aL very low cosL per lengLh ln a wlde
range of dlameLers Surface cleanlng ls
easlly accompllshed uslng acld soluLlons
(eg LreaLmenL wlLh phosphorlc acld
removes all buL a few Lraces of Lhe naLlve
oxlde) and leaves behlnd a sllghLly
oxldlzed surface LhaL ls well sulLed Lo
growLh of a dlelecLrlc layer Some
prellmlnary sLudles wlll be aLLempLed
uslng gold wlres because gold surfaces
are very noble and are easlly modlfled
uslng organosulfur reagenLs Cold wlres
are noL pracLlcal for LexLllebased flbers
buL Lhey may be useful for earlysLage developmenL work Work wlLh commerclally
avallable carbon flbers ls also planned Carbon ls hlghly conducLlve and well sulLed for
use as a flber capaclLor subsLraLe alLhough some aLLenLlon Lo Lhe carbon surface chemlsLry
wlll be necessary Lo promoLe growLh of homogeneous plnholefree dlelecLrlc fllms 1hls
work wlll be pursued laLer afLer prellmlnary work wlLh meLal flbers ls compleLed
As an aslde we noLe Lhe posslblllLy of uslng conducLlve polymer flbers as Lhe cenLral
conducLlve subsLraLe ln a flber capaclLor Cne of us has prlor experlence ls uslng splnnlng
Lechnlques Lo prepare hollow flbers made from conducLlve polyanlllne (Anl)1 an
example ls shown ln llgure 2 1he Lechnlques used Lo make Lhe flber shown ln llgure 2
could be easlly exLended Lo prepare solld flbers 1hls approach could ulLlmaLely be used
Lo prepare allpolymer flber capaclLors lf lL ls coupled wlLh some new ldeas we have for
polymer dlelecLrlcs whlch are descrlbed below
ulelecLrlc Lhln fllms on Lhe flbers
1he meLal oxldes LhaL make Lhe mosL sense as hlghpermlLLlvlLy dlelecLrlcs for capaclLors
are LanLalum nloblum hafnlum zlrconlum lanLhanum and LlLanlum oxldes
ermlLLlvlLles are beLween 13 and 30 for Lhese oxldes wlLh exacL values varylng among
sources 1hese are hlgh values whlch wlll resulL ln hlgh capaclLances and hlgh energy
sLorage denslLy MosL research ln ceramlc capaclLors ls focused on Lhese meLal oxldes
and relaLed maLerlals
Cur approach ls Lo use soluLlon solgel Lechnlques Lo prepare ulLraLhln fllms of Lhese
ceramlc meLal oxldes on conducLlve flbers We have made some very prellmlnary
llgure 2 A hollow flber of conducLlve polyanlllne
(Anl) produced by splnnlng 1hls phoLo ls from
earller work (2003) however slmllar Lechnlques wlll
be used Lo produce solld Anl flbers sulLable for use
as conducLlve subsLraLes for flber capaclLor
fabrlcaLlonn1C ro[ecL M06CL07
age 6 of 9
naLlonal 1exLlle CenLer Annual 8eporL november 2006
aLLempLs aL uslng solgel Lechnlques Lo prepare ceramlc oxlde coaLlngs on meLal wlres
1hese early experlmenLs were performed on Lhe benchLop or ln a rudlmenLary glove box
fllled wlLh house nlLrogen buL wlLhouL gas reclrculaLlon 1he experlmenLs mosLly falled
due Lo Lhe Lendency of Lhe solgel precursor soluLlons Lo become cloudy and form oxlde
preclplLaLes probably because of conLamlnaLlon by advenLlLlous waLer lL ls clear LhaL Lhls
work wlll requlre greaL care Lo avold waLer conLamlnaLlon We are ln Lhe process of
seLLlng up a dry box LhaL wlll be used for pro[ecL work wlLh solgel chemlsLry Lhls comlng
year
8ecenLly we have consldered an alLernaLlve approach lnvolvlng ulLraLhln polymer fllms as
dlelecLrlcs olymer fllms have long been used as capaclLor dlelecLrlcs A prlnclple
advanLage of polymers as dlelecLrlcs ls Lhelr ease of fabrlcaLlon as Lhln fllms A
dlsadvanLage ls LhaL Lhey have relaLlvely low permlLLlvlLles eg values above 40 are rare
Lven so polymer dlelecLrlcs may be well sulLed Lo Lhe presenL pro[ecL and we plan Lo LesL
some approaches uslng ulLraLhln polymer fllms as dlelecLrlcs
Cne approach we propose for LesLlng lnvolves sequenLlal layerbylayer deposlLlon of
polyelecLrolyLes of opposlLe charge 1hls approach ls lllusLraLed ln llgure 3 ln brlef lL
lnvolves an lnlLlal LreaLmenL of Lhe subsLraLe Lo lnLroduce a surface charge followed by a
serles of alLernaLlng LreaLmenLs wlLh soluLlons of polyelecLrolyLes Lach polyelecLrolyLe
LreaLmenL resulLs ln deposlLlon of a polymer layer and sequenLlal LreaLmenLs produce
mulLlple layers of conLrolled Lhlckness lllm Lhlcknesses beLween a few nanomeLers and
a few hundred nanomeLers have been achleved ln Lhls way
1able 1 presenLs sLrucLures for flve polyelecLrolyLes LhaL have been used Lo accompllsh
layerbylayer coaLlng on solld subsLraLes We wlll LesL Lhese and also some oLher
A 8
C
8epeaL
llgure 3 A sLraLegy for coaLlng a conducLlve flber wlLh an ulLraLhln conformal layer of a polymer
dlelecLrlc (A) 1reaLmenL wlLh a soluLlon of a caLlonlc polymer aL low lonlc sLrengLh resulLs ln flber
coaLlng wlLh an ulLraLhln polycaLlonlc layer (8) SubsequenL LreaLmenL wlLh a soluLlon of an anlonlc
polymer adds Lo Lhe polymer layer Lhlckness (C) 8epeaLlng sLeps A and 8 mulLlple Llmes resulLs ln
conLrolled growLh of a polymer layer LhaL ls lnherenLly conformal and plnholefree and for whlch
Lhlckness can be easlly conLrolled ln Lhe 101000 nm reglme n1C ro[ecL M06CL07
age 7 of 9
naLlonal 1exLlle CenLer Annual 8eporL november 2006
polyelecLrolyLes wlLh a focus on Lhelr ablllLy Lo form conformal coaLlngs on conducLlve
solld subsLraLes by Lhe layer by layer approach and also on Lhe dlelecLrlc properLles of Lhe
resulLlng fllms when overcoaLed wlLh a conducLlve layer
1able 1 olyelecLrolyLes for layerbylayer growLh of polymer dlelecLrlcs
olyelecLrolyLes SLrucLure 8eference
s
oly (sodlum 4sLyrenesulfonaLe) 12
oly(allylamlne hydrochlorlde) 2 3
oly(acryllc acld) 2
oly(dlallyldlmeLhyl ammonlum
chlorlde)
1
olyeLhylenelmlne 4
8eferences
1 uan Ll Wang xl eL al MaLerlal sclence and englneerlng C 11 (2000) 117119
2 uursLock M 8ubner M Langmulr 2001 17 78637872
3 uanlel L leldhelm kaLherlne C Crabar Mlchael ! naLan* and 1homas L
Mallouk* ! Am Chem Soc 1996 118 76407641
4 Culllaume Perlemll !Cu8nAL Cl CPLMlCAL P?SlCS vCLuML 120
nuM8L8 19 93769381
ConducLlve ouLer coaLlngs
We plan Lo lnvesLlgaLe elecLronlcally conducLlve polymers as conducLlve ouLer coaLlngs
for flber capaclLors olypyrrole polyanlllne and polyLhlophene derlvaLlves especlally n1C ro[ecL M06
CL07
age 8 of 9
naLlonal 1exLlle CenLer Annual 8eporL november 2006
poly(34eLhylenedloxyLhlophene) (LuC1) ln Lhe doped form wlLh poly(4sLyrene
sulfonaLe) as couLerlon have all been used as elecLrodes ln capaclLors13 14 and wlll be
lnvesLlgaLed 1he laLLer ls avallable commerclally under Lhe Lrade name 8ayLron"
MeasuremenLs
CapaclLance wlll be measured uslng
sLandard elecLrochemlcal lmpedance
specLroscopy meLhods and relaLed
Lechnlques Cell deslgns wlll lncorporaLe
Lhe flber geomeLry so as Lo provlde lowlmpedance elecLrlcal conLacL Lo boLh Lhe
lnner flber and Lhe ouLer conducLlve
polymer phase Llquld mercury conLacLs
such as LhaL lllusLraLed ln llgure 4 wlll be
used for earlysLage measuremenLs and
laLer measuremenLs belng made uslng
conducLlve epoxy pasLes or palnLs conLalnlng meLal or carbon parLlcles Lo provlde
elecLrlcal conducLlon ln Lhe laLe pro[ecL sLages we anLlclpaLe worklng wlLh Lhe lndusLrlal
advlsors regardlng sLraLegles for maklng elecLrlcal conLacL ln flber bundles and ln