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Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012 !"#10$

Contents lists a%aila&le at Sci'erse Science irect

Colloids and Surfaces A: Physicochemical andEngineering Aspects

) o u r n a l h o m e p a g e : * * * . e l s e % i e r . c o m + l o c a t e + c o l s u r f a

,a&rication of conducti%e polymer-coated sulfur composite cathode materials&ased on layer-&y-layer assem&ly for rechargea&le lithium#sulfur &atteries

i uan

/ iachun u/ enyuan iu/ Ping uang/ ushang ang/ 3hichao iuorth*est 5nstitute of uclear 6echnology/ 7i8an/ Shaan9i 10024/ China

h i g h l i g h t s g r a p h i c a l a & s t r a c t A no%el conducti%e polymer-coatedsulfur cathode in i+S &attery *asfa&ricated.

& assem&ly techni;ue *as introducedto encapsulate sulfurcathode in i+S &attery.Polymers *ere coated on the surface of sulfur only &y physical interaction.6he as-prepared sulfur represents a

*ell conducti%ity of 0.2$ S cm ay 2012=ecei%ed in re%ised form 2$ uly 2012 Accepted ? August 2012

A%aila&le online 2" August 2012

@ey*ords:ithium+sulfur &atteries

Sulfur cathodeayer-&y-layer assem&ly

Conducti%e polymer

a & s t r ac t

ithium#sulfur &atteryis apromisingenergystoragesystem dueto its highspecificenergydensity/ lo*cost anden%ironmental friendliness.

ayer-&y-layer ( &assem&lytechni;ue isintroduced asa simplemethod tofa&ricatepolymer-coated sulfur

cathode materials for rechargea&le lithium#sulfur &atteries. Conducti%e polyaniline (PA 5 *ere

assem&led on the outer shell of sulfur particles topro%ide an electron conducting paths for the chargeand discharge of lithium#sulfur &attery. 6he lo*permea&ility of sulfur shells *as o&tained &yassem&ling the enough num&er of polyelectrolyte&ilayers. A crosslin er and heat treatment *ereutiliBed to further reduce its permea&ility. 6heassem&led polymer shells can &e e9pected to &e

permea&le for i and slo*ly or hardly for sulfur and polysulfide during charge and dischargeprocess. 6he o&tained sulfur composite cathodematerials *ere characteriBed &y four-point pro&einstru-ment/ scanning electron microscopy (SE> /transmission electron microscopy (6E> / 7-raydiffraction (7= patterns and ,ourier transforminfrared (,65= spectroscopy. 6he resultsdemonstrated polymers ha%e &een coated on thesurface of sulfur only &y physical interaction andha%e no effect on sulfur. 6he conducti%e polymer-coated sulfur cathode also represents a *ell

conducti%ity of 0.2$ S cm oreo%er/ after coated&y polymers/ the crystal structure of sulfur still

eeps its orthorhom&ic corresponding to

cyclooctasulfur molecule (S " .

D 2012 Else%ier .'. All rights reser%ed.

1. Introduction

6he de%elopment of rechargea&le

&atteries *ith a high energy density and longcycle life is currently of great importance/ as

theycanpo*er anincre

asingly

di%erse range of applications/ from

1 Correspon

ding author.

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0!2 - ? +I # see front matter D 2012

Else%ier .'. All rights reser%ed.http:++d9.doi.org+10.101F+).colsurfa.2012.0".0$$

microchipsfor small-siBeelectr onicde%ices/ to

po*er sources for electr ical %ehicles.

ithium#sulfur &atteryconsisting of sulfur as thecathodes and lithium asthe anodes J1/2K is %eryattracti%e &ecause of itshigh theoretical specificcapacity of 1F ? mAh g


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. uan et al. + Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103 !!

property. 6hese pro&lems are attri&uted to the insulatingnature of sulfur JFK and the dissolution of lithium polysulfides

(Sn2< / n L 4 formed during discharged process into the

li;uid electrolytes J?/ #10K. 6he insulating nature of sulfur pre%ents full discharge of a i+S &attery *ith a 100M sulfur positi%e electrode at room tem-perature. 6he dissolution of polysulfides can cause self-discharge and poor electronic

conducti%ity of i+S &attery/ resulting in a rapid capacityfading of lithium &attery during cycling. As one alternati%ely resol%ed method/ the cathode

materi-als can &e *ell com&ined *ith electrical and ionicconducting agent/ such as the electro-polymeriBedconducti%e polyaniline (PA 5 and polypyrrole (PPN / *hich*ould impro%e the &attery8s rechargea&ility J11#1 K.

esides/ the use of a&sor&ing agent/ such as aluminumo9ide/ silicates/ %anadium o9ides and transition chalco-genides J1"K/ can effecti%ely pre%ent the polysulfidesdissolution due to their large surface. o*e%er/ theseadsor&ing materials are not desira&le as additi%e for lithium+sulfur cells due to their insu-lating property. 6headdition of linear car&on materials/ such as multi-*alledcar&on nanotu&es (> 6s and car&on nanofi&ers/ intosulfur cathode as a&sor&ing agent can also impro%e cyclelife of lithium#sulfur &attery/ as they present an effecti%eelectron con-ducti%ity and a sta&le net*or -li e structure of sulfur cathode. o*e%er/ they are difficult to commercialiBedue to their high cost and the comple9ity of themanufacturing process. PA 5 and PPN *ith specialmorphology can *ell &e used as conducti%e addi-ti%es/distri&ution agents and a&sor&ing agents to enhance theelectrochemical performance of sulfur. So/ *e targeted our *or on fa&ricating sulfur composite cathode materialscoated *ith elec-tronically conducti%e polymer matri9.

5n our pre%ious *or / layer-&y-layer ( & assem&lytechni;ue has &een successfully applied in the fa&ricationof %arious function-aliBed microcapsules &ased on the

different interaction forces/ such as electrostatic interactionJ1!#2$K and co%alent &ond J24#$0K. 6he assem&ledcapsules ha%e *ell-controlled siBe/ shape/ and *allthic ness. A *ide range of components such as natural or syn-thetic macromolecules/ nanoparticles and proteins J$1Kcan &e chosen as coating materials. 6he *all compositioncan &e readily changed to ad)ust their physicochemicalproperty and perme-a&ility. 6he typical composition aremainly positi%ely charged poly(allylamine hydrochloride(PA and negati%ely charged poly(styrenesulfonatesodium salt (PSS J1!/20K. >oreo%er/ the PA +PSScapsules shell has &een found to &e a&le to s*ell andshrin in response to temperature J20K. eporatti et al.

demonstrated that during the heating at 0 O C for 2 h/ thePA +PSS capsules shrin remar a&ly and the *all&ecomes thic er. ur pre%ious *or also sho*ed that four &ilayers of hollo* P A >AC+PSS capsules at high

temperature (?? and 1 O C are impermea&le for F-C, (> *$ $.F2 a G &ut at lo* temperature they are permea&leJ22K.

6he cross-lin ing agent/ such as glutaraldehyde (QA /can &e used to immo&iliBe %arious macromolecules. 6hecross-lin ed macromolecules can sho* a higher sta&ilityo%er a &road range of p and temperature conditions/ anda more compact structure J24/$2K. 6hus/ this immo&iliBationmethod is attracti%e in its sim-plicity and ro&ustness/ as itoffers a good route for enhancing the dense of particleshells.

erein/ *e e9plored a facile and controlla&le a%enue tofa&ricate no%el sulfur composite materials *ith impro%ed

electrochemical performance inlithium#sulfur &atteries. 6he positi%elycharged poly(allylaminehydrochloride (PA and negati%elycharged poly(styrenesulfonatesodium salt (PSS *ere firstalternately adsor&ed on the surfaceof sulfur for 10 &ilayers. 6hen/ the

aniline monomers *ere polymeriBedto a conducti%e polyaniline on theouter shell of polymer-coated sulfur &y the o9idation of ammoniumpersulphate (APS . 6he *allthic ness of sulfur composite materi-als can &e *ell controlled &yad)usting the num&er of assem&ledlayers. 5n order to impro%e thepermea&ility of sulfur shells/ the

glutaraldehyde (QA *as further utiliBed to immo&iliBe the shells &y theco%alent &ond &et*een the aldehydegroups of QA *ith the free aminosites of PA . 6he heat treatment *asperformed to o&tain a thic er andmore contracti%e sulfur shell.

2. Experimental

2.1. >aterials

Polyethyleneimine (PE5/ > * ?0#100 a / poly(allylaminehydrochloride (PA (> * 0 a /poly(styrenesulfonate sodium salt(PSS (> * 0 a / gultaraldehyde(QA and the *ater-solu&lepolypyrrole (PPN (? *tM in *aterdoped *ith organic acid *erepurchased from Sigma#Aldrich. 6heaniline monomer *as used *ith

further purification &y decompresseddistillation and then stored at 0#? O C.6he *ater used in all e9periments*as prepared in a three-stage>illipore >illi-R Plus 1"? purificationsystem and had a resisti%ity higher than 1".2 > cm.

2.2. Assem&ly ofpolyelectrolyte multilayers onthe surface of sulfur particles

Sulfur particles *ere separatelydispersed in PE5 solution (1 mg+m in0.? > aCl and allo*ed to adsor& for $0 min. 6hen e9cess polyelectrolytes*ere remo%ed &y centrifugation andthree times *ashing *ith 0.? > aCl.Su&se;uently the a&o%e suspen-sions *ere alternately dispersed inPA and PSS solution (2 mg+m in0.? > aCl for another $0 min/follo*ed &y three times *ashing in0.? > aCl. After the assem&ly of adesired num&er of PA +PSS layer/the coated particles *ere thendispersed in ?M glutaraldehyde (QAa;ueous solution for $0 min. ,inallythese sample suspensions *ereincu&ated at the high temperature for 20 min.

2.$. Preparation of conducti%e PA 5and PPN shells

5n a typical procedure/ theprepared polymer-coated sulfur par-ticles a;ueous dispersion *as addedinto the aniline monomer solutionmi9ed *ith 1 > hydrochloric acid( Cl under stirring. After $0 min/ thee;ui%alent num&er of moles of 22."

*tM a;ue-ous ammoniumpersulphate (APS solution (*ith


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respect to aniline *as slo*ly added/ follo*ed &y an

o9idati%e polymeriBation at 0#$ O C. 6he reaction *ascarried out for 24 h. 6he resultant green solid/PA 5+polymer-coated sulfur particles/ *ere o&tained &ycen-trifugation and *ashed *ith *ater and ethanolthoroughly to remo%e e9cess ions and monomers. 6heprocedure *as repeated to increase the PA 5 content. 6hefinal product *as dried under %acuum at am&ienttemperature for 24 h. 6he *hole e9periments *ereperformed under the nitrogen atmosphere. 6he conducti%epolypyrrole (PPN shells *ere prepared through aelectrostatic interaction of the negati%ely charged PPN on

the positi%ely charged outer shell of

(PA +PSS n+PA -coated sulfur particles. 6he resultant gray solid *asdried for further characteriBation andtesting.

2.4. ,our-point pro&e instrument

Conducti%ity measurements of thecompressed piece of dry po*der *ere performed using a standard

four-point pro&e tech-ni;ue/ S3"2( aishen 6echnologies/ China / atroom temperature J$$K.

2.?. SE>

Scanning electron microscopy(SE> *as applied to o&ser%e thesurface morphology of sulfur particles. Samples *ere sputtered


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100 . uan et al. + Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103

Scheme 1. Schematic illustration of the fa&rication of conducti%e polymer-coated sulfur as cathode for lithium#sulfur &atteries &y layer-&y-layer assem&ly.

*ith gold and measured using a Ruanta F00,EQ instrument (,E5/ American at anoperation %oltage of $.0 e'.

2.F. 6E>

,or transmission electron microscopy(6E> o&ser%ation/ the sulfur particles after coated &y (PA +PSS 10 PA 5 *ereredispersed in ethanol &y ultrasonic treatmentand dropped on car&on#copper grids. 6E>images *ere collected &y using a E E>1011 , micro-scope *or ing at 100 '.

2. . 7=

7-ray diffraction (7= patterns *erecollected on a +>A7-2400 po*der 7-raydiffractmeter operating at 40 ' and $0 mAand using Cu-@ radiation ( 0.1?40F nm .

2.". ,65=

,ourier transform infrared (,65=spectrum *as measured on a >agna ?0spectrometer ( icolet/ American using @ r pressed dis s.

3. Results and discussion

6o search for higher capacity and &etter rate performance of lithium#sulfur &attery/ thefa&rication of appropriate composite cathodematerials is imperati%e. ere/ *e controlla&lysynthe-siBed the conducti%e polymer-coatedsulfur composite materials &ased on layer-&y-layer assem&ly techni;ue/ as sho*n inScheme 1 . 6he positi%ely chargedpoly(allylamine hydrochloride (PA andnegati%ely charged poly(styrenesulfonatesodium salt (PSS *ere alternati%elyadsor&ed on the surface of sulfur particles &yelec-trostatic interaction. 6he *all thic nessof sulfur particles can &e *ell controlled &yad)usting the num&er of adsorption layer/accompanied *ith a controlla&le permea&ility.5n present *or / 10 &ilayers of polymers *ereassem&led to o&tain the dense sulfur shells.>oreo%er/ it has &een found that thecrosslin ing J24/$2K and heat treatment

J22/$4/$?K can decrease thepermea&ility of capsule*alls/ resulting from therearrangement of thepolymer chains induced &yheating and crosslin ing intoa more preferred structure.6his rearrangement processis accompanied &y *all

thic ening/ condensation of polyelectrolyte and thus adistinct decrease of poresiBe. So polymer-coatedsulfur particles *ere su&-se;uently crosslin ed &yglutaraldehyde (QA and

*ere heated to around 0 O

C. 5t can &e e9pected thatthe o&tained polymer shellsof sulfur are permea&le for %ery small molecular *eightof lithium ions &et*een theinterior and e9terior/ &ut

slo*ly or hardly per-mea&lefor sulfur and polysulfide.Scheme 1 alsoschematically illustrates therecharged process of sulfur as a cathode. uringdischarge and chargeprocesses of i+S &atteries/the redo9 cou-ple reaction

of lithium *ith sulfur to i 2 S/

1F i S " T " i 2 S/ can

Fig. 1. 6he photos of pure sulfur (yello* / PA 5-coated sulfur (green and PPN-coated sulfur (gray composite materials as-prepared. (,or interpretation of thereferences to color in this figurelegend/ the reader is referred tothe *e& %ersion of the article.

occur/ accompanied &yreaction intermediates/ thesolu&le poly-sulfide anions.6he e9istence of thepolysulfide can cause theacti%e mass loss of cathodeand anode/ *hich areattri&uted to polysul-fides8migration into the electrolyteand finally precipitates onthe electrode surface. o*/the as-prepared polymers

shells on the surface of sulfur *ill effecti%ely controlthe slo* release of sulfur and polysulfide into theelectrolyte solutions. ,inally/to o&tain a re%ersi&leelectrochemical reaction athigh current rates/ conduc-ti%e PA 5 and PPN areassem&led on the outer surface of electricalinsulating sulfur particles &yelectrostatic interaction *ithoppo-sitely chargedpolyelectrolytes. As a result/a no%el sulfur compositematerials *ith an impro%edelectronic conducti%ity andthe dense shells *ereo&tained/ *hich *illeffecti%ely enhanceelectrochem-icalperformance of lithium#sulfur &attery.

,ig. 1 sho*s the photosof pure sulfur (yello* / PA 5-coated sulfur (green andPPN-coated sulfur (graycomposite materials as-prepared. 5n present study/


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the synthesis of polyaniline is &y o9idati%epolymeriBation of aniline monomer *ithammonium pero9odisulfate as an o9idant.6he components are &oth dissol%ed in 1 >hydrochloric acid and slo*ly added to eachother/ consid-ering the e9othermic reaction.Polyaniline can &e found in one of threeidealiBed o9idation states sho*ing differentcolor and con-ducti%ity J$FK. ne is the fullyreduced state/ leucoemeraldine/ *ith*hite+clear or colorless. Second is the fullyo9idated state *ith imine lin s instead of amine lin s/ pernigraniline/ *ith &lue+%iolet.

Another is the intermediate state/ emeraldine/*ith green for the emeraldine salt and &lue for emeraldine &ase. Emeraldine form of polyaniline/ often referred to as emeraldine&ase/ is neutral/ if doped it is calledemeraldine salt/ *ith the imine nitrogensprotonated &y an acid. Emeraldine &ase isregarded as the most useful form of

polyaniline due to its highsta&ility at roomtemperature and the factthat/ upon doping *ith acid/the resulting emeraldine saltform of polyaniline iselectrically conducting J$ K.

eucoemeraldine andpernigraniline are poor conductors/ e%en *hendoping *ith an acid. ere/the green sulfur po*der can&e seen from the center tu&e (,ig. 1 / *hichdemonstrated the highlyconducti%e emeraldine salt&y doped *ith acid *assuccessfully o&tained insulfur materials. 5n the righttu&e (,ig. 1 / the gray sulfur po*der sho*s the presence

of PPN *ith *ell conducti%ityin sulfur materials. ,or comparison/ pure sulfur po*der is sho*n in the lefttu&e (,ig. 1 .

5n the present *or /considering the &etter utiliBation of sul-fur ascathodes/ commercial sulfur

po*der *ith a large siBea&o%e 10 m *as pre-treatedinto a smaller siBe &elo* 10m &y sie%ing andmechanical milling. Also/ thesmall sulfur particles aremore fa%ora&le to maintainthe intact encapsulation of polymer after the


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. uan et al. + Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103

Fig. 2. SE> images of (a pure sulfur particles &efore milling/ (& pure sulfur particles after milling/ (c (PA +PSS 10 PA 5-coated

sulfur particles and (d (PA +PSS F (PA +PPN 4 - coated sulfur particles. 6he inset is higher magnification of a single sulfur particle.5ts E 7 analysis is sho*n in the right of image.

follo*ing mulling for preparing sulfur cathodes. 6hemorphology of sulfur particles &efore and after coated

&y polymers *as e9amined &y &oth SE> and 6E>.,ig. 2 a and & sho*s the SE> morpholo-gies of sulfur particles &efore and after milling/ respecti%ely. 5t can&e seen that the siBe of sulfur particles after milled*as o&%iously decreased and that the surface *asmore glaBed. Compared *ith pure sulfur particles/ thesulfur particles layer-&y-layer encapsu-lated &ypolymers sho* a more dense and rough surface

structure/ as sho*n in ,ig. 2 c and d for (PA +PSS 10

PA 5-coated sulfur and (PA +PSS F (PA +PPN 4-coated sulfur/ respecti%ely. 6he differences of surfacemorphologies can &e attri&uted to the *ell coat of poly-mers on the surface of sulfur particles. 6hehigher magnification of a single sulfur particle ispro%ided in the inset. ,rom its corresponding E 7analysis/ it further pro%ed the e9istence of the

polymers on the sulfur particles. 6E> image of

a selected (PA +PSS 10PA 5-coated sulfur particles also displaysthe successful coatingof polymer films(arro*s / sho*n in ,ig.$. 6he inset sho*s itshigher magnification.

6o no* theelectroacti%ity of PA 5after polymeriBed andassem&led &yelectrostatic interaction*ith polyelectrolytes/the

conducti%ity ( of as-prepared sulfur composite materials

*as cal-culated from thecorrelati%e e;uation.6he electric resisti%ity (*as first determined &yfour-point pro&etechni;ue andcalculated according toE;. (1

0 U GW

U Dd

(1S s

*here 0 is the measuredelectric resisti%ity/Q( +S is the cor-rection coefficient of sample thic ness and


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(d+s is the correction coefficient of sample shapeand measured position. 6he correction coefficient for Q and can &e o&tained from the reference dataaccording to the sample thic ness/ diameter andmeasured posi-tion. 6hen/ the conducti%ity ( *ascalculated from the reciprocal of resisti%ity ( . As aresult/ for PA 5-coated sulfur materials/ theconductance is around 0.2$ S cm


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102 . uan et al. + Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103

Fig. 3. 6E> images of (PA +PSS 10 PA 5-coated sulfur particles. 6he inset is its higher magnification.

materials in lithium#sulfur &attery. 6he PPN-coated sulfur cathode materials also possessa *ell electric conducti%ity of 0.00F S cm


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stretching %i&ration is at 11 ? cm


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. uan et al. + Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 98103 10$

,c-no ledgments

6his *or is financially supported &y theational ature Sci-ence ,oundation of

China (2110$1$! .

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