batteries

Article
Sol-Gel Synthesized Antimony Anodes for
Sodium-Ion Batteries: Identifying Key Parameters
for Optimization
Nicholas E. Drewett 1 , Juan Luis Gmez-Cmer 1 , Begoa Acebedo 1 , Montserrat Galceran 1

and Tefilo Rojo 1 , 2 , *

1 CIC energiGUNE, Parque Tecnolgico de lava, 01510 Miano, Spain;
ndrewett@cicenergigune.com (N.E.D.); jlgomez@cicenergigune.com (J.L.G.-C.);
bacebedo@cicenergigune.com (B.A.); mgalceran@cicenergigune.com (M.G.)
2 Departamento de Qumica Inorgnica, Universidad del Pas Vasco UPV/EHU, P.O. Box. 644,
48080 Bilbao, Spain
* Correspondence: trojo@cicenergigune.com; Tel.: +34-945-297-108
Academic Editor: Yutaka Moritomo
Received: 30 March 2017; Accepted: 26 June 2017; Published: 30 June 2017

Abstract: The potentially high gravimetric capacities of intermetallic anodes, coupled with the
low cost and readily available materials used in sodium-ion batteries, has generated interest in
antimonyan anode capable of alloying with sodium. However, presently there are few synthetic
routes to antimony particles for use in sodium-ion batteries. One pot, sol-gel synthetic routes
from readily available, chloride-free precursors have been developed. The resulting products have
been characterized and, from this data, several key parameters optimization have been identified
and are presented here. Finally, using this information, some initial optimization has been carried
out, which resulted in minor improvements to the physical and electrochemical properties of the
resulting product.

Keywords: intermetallic antimony anode; sodium-ion battery; sol-gel synthesis; electrochemistry;

synthesis

1. Introduction
Currently, modern society has a strong dependence on the ability to generate, store, and manage
energy, andfrom transportation and portable electronic devices to stationary and grid storagealkali
metal-ion batteries have proven an attractive option in meeting these ever-increasing demands.
Furthermore, there is considerable impetus to develop lithium- and sodium-ion batteries as their
versatile nature and wide range of tailorable properties make them well-suited to optimization for
specific applications [111]. While lithium-ion batteries have proven a versatile and popular choice of
energy storage system, growing demand combined with the geographic constraints on lithium natural
resources has generated considerable interest in developing beyond lithium systems. Sodium-ion
batteries consist of abundant, low cost, readily available materials and exhibit similar insertion
chemistries to lithium-ion batteries. As a consequence of these attractive properties, sodium-ion
batteries are currently regarded as an emerging technology that may compliment, or even substitute,
lithium-ion technology. However, continuing improvements to gravimetric energy densities are
necessary in order to increase the competitiveness of these systems. Thus, developing anode and
cathode systems with higher specific charges and energy densities is a crucial area of research. Due to
the potentially achievable high gravimetric capacities, there has been interest in using intermetallic
particles in negative electrodes (anodes). However, these high gravimetric capacities are also frequently

Batteries 2017, 3, 20; doi:10.3390/batteries3030020 www.mdpi.com/journal/batteries

Batteries 2017, 3, 20 2 of 16

accompanied by large volume changes occurring during sodiation/desodiation, which can lead to
loss of electrical contact within the anode and pulverization of the active particles. This pulverization
may, in turn, result in damage to the surface of the intermetallic particles, leading to continuous
solid-electrolyte interphase (SEI) formation/breaking and irreversible capacity loss [1215].
However, despite the drawbacks, the possibility of high electrochemical performance still
generates interest in developing and improving these types of materials, particularly for sodium-ion
batteries [16,17].
Intermetallic antimony (Sb) has a range of properties that make it a potentially attractive anode
materialit can alloy with sodium or lithium with a theoretical gravimetric capacity of 660 mAh g1
Sb (based on the capacity of M3 Sb), and even bulk Sb is relatively attractive (with reversibility at low
to moderate current density) [1720].
However, the stress and strain caused by volumetric changes during cycling remains a key issue
for Sb, and this will require some degree of mitigation in order to obtain an improved electrochemical
performance [2123]. Nevertheless, there has been a significant level of interest in using Sb in both its
pure form and as the basis of a composite anode material.
A range of approaches to improving Sb anode performance have been considered, such as
the development of novel micro- and nano-structures [17,21,22] or modifications of its crystalline
nature [23]. Stable and reversible sodiation has been demonstrated for bulk antimony and in thin
films [18,20], with work also having been carried out into sodiation of antimony/carbon fibers
synthesized by electrospinning [24] or by oxidative polymerization [25]. Excellent cycle life has
been demonstrated for Sb/C composites prepared by mechanical milling [26] or spray pyrolysis [27].
Recently, nano-sized antimony particles were synthesized and, after additional processing, were
able to demonstrate excellent rate capability and cyclability during both sodiation and lithiation [19].
However, these also exhibited poorer coulombic efficiencies than bulk antimony in the initial cycle,
which has been attributed to the larger surface area of the nanomaterials leading to increased
decomposition of electrolyte during the formation of the SEI layer [16,19]. This may suggest that
antimony particles whose size is between that of the nano- and bulk materials could have improved
characteristics compared to both. Thus, the ability to tailor the size and morphology of the antimony
particles during synthesis may well be significant.
In order to further explore the use of Sb as an intermetallic anode, it will first be necessary to
investigate and optimize the material at the lab-scale. However, while currently there are several
synthetic routes to choose from which lead to Sb materials with excellent properties, these frequently
involve challenging conditions such as time consuming, continuous ball milling [28] or a complex,
multistep colloidal route followed by ball milling [19]. Moreover, many syntheses involve the use of
antimony chloride as the antimony source, which in turn introduces chloride species contaminants
(which are both difficult to remove and environmentally unfriendly). Thus, it would seem reasonable
to propose that there is some use in developing a faster, easier route to synthesizing Sb particles.
In this study, we present an investigation into key parameters for developing a simple sol-gel route,
using readily available and halogen-free precursors to Sb particles for use in sodium-ion batteries.

2. Results

2.1. Antimony Acetate/Acetic Acid Synthetic Route

Previous research into autoignition self-combustion reactions has shown that it is possible to
form particles of the pure metal by a routine sol-gel method [29]. This is a result of reductive gases
formed from the reaction between citric acid and the nitrate salts of the metals, and reducing in situ
the metal ion to its 0+ charge state. While there are few stable and potentially soluble antimony
precursors suitable for this work, one objective was to avoid the presence of chloride ions (which
typically result from the widely used antimony chloride precursor). Furthermore, it was desirable to
make use of readily available chemicals. Thus, antimony acetate was selected as the antimony source
Batteries 2017, 3, 20 3 of 16

and ammonium nitrate as the nitrate salt. Since the reducing gases are generated in situ as a result of
Batteries 2017, 3, 20 3 of 16
the autoignition self-combustion reaction between ammonium nitrate (Ox) and citric acid (CA), it is
possible tothceoanuttrooigl ntihtieondseeglfrecoemobfursetidonucretiaoctniob
n ybeatw
lt eeninagmtmhoenO
iux
m:CniA
trartae t(iO
ox. ) and citric acid (CA), it is
Thus,poth sseiblreattoio cont o froal nthteim
deogn
reye oto f readnutcitmion
onby alteoxriing
de thine Ox:eCA
th raatilo.product may be optimized, and
fin
Thus, the ratio of antimony to antimony oxid e in the final product may be optimized, and
subsequently qu an tified th r ugh the use of powder X-ray diffrac tometry (P XRD) as seen i Figure 1a.
subsequently quantified through the use of powder Xray diffractometry (PXRD) as seen in Figure 1a.

Figure 1. (a) Powder Xray diffractometry (PXRD) patterns of materials synthesized with varying
Figure 1. antimony
(a) Powder X-ray
acetate diffractometry
(SbAc), citric acid (CA),(PXRD) patterns
and ammonium of materials
nitrate (Ox) ratios.synthesized
Valentinite Sb2withO3 is varying
antimony macaerkteadtew(iS
thb*A
; (c
b)),ac
nidtr(icc) saccid
annin(C
geAle)c,traonndmaicm
rom
scoopn
yi(u
Sm
EMn) im
trate (oO
f Sxb) (rSa
btAio
c:s
C.AV
:Oaxl
en1t:3in
:2i).te Sb2 O3 is
marked with *; (b) and (c) scanning electron microscopy (SEM) images of Sb (SbAc:CA:Ox1:3:2).
Initially, prior to optimization, a high ratio of SbAc was used. However, examination of the
PXRD patterns shows that the products with the SbAc:CA:Ox molar ratios of 1:0.3:0.3 and 1:0.3:0.1
Initialdly
o,nportiaoprpteoarotp oth im
aviezatiyoann,tiamhoingyhmreattailopo refsSenbtA. Tchw is a
wsau s slie
kd
el.y H duoewtoevtheer,loew xaam mionuanttiofnco itrficthe PXRD
patterns sh acoid
wpsreth seant tinhethpe rgo eldluimcits inwg tihthe atmhoeuSnbt A of cin
:CsA itu:Orex dumcinoglagrasreastifosmoefd,1a:0 nd.3t:h0u.3s tahnedre1d:u0c.t3io:0n.1 do not
appear to ohf ath vee aanntiy
moannytiim ono . Inny
term esetitnagllyp, rwehsielent. eTPh XiRsDwpaasttelrinkeolfythd eu 1e:0.t3o
:0.t3hperold ouwct acom rroesupnotndosf tcoitric acid
pur sena rmon te Sb2O3, that f the 1:0.3:0.3 product exhibits additional peaks (marked with *) which
present inappear
the geto l lcorrespond
imiting the am ount of in situ red ucing gase s formed, an d thus th e reduction of
to valentinite Sb2O3. While Sb2O3 may be used as an anode material, the
the antimocn onversion reaction betweew
y i o n . In t e re s tin g ly , n shoidleiutmheioP nsXaR nD peaottxeidrn
d th e loeafdtshteo 1 a :h0i.g3h:0ir.3
repverrosid
bulecctacpoacrirteyslp
ososnod n s to pure
senarmonthitee fSirbst2 O cy3c,leth [3a0t3o4f]. tThheis1:m0i.g3h:0t .3 bepurnoddeu sic
ratbelexh inibaitfsulal dcdelil,tisoonal dp ite
ioankasl o(mptiam rikzeatdionww ithas *) which
appear to ucnodrerretaskpeonnsod atsotovoabltean intianpituereSSbb2 pOrod uct. The PXRD pattern of Sb (SbAc:CA:Ox1:1:2) shows
3. W hile Sb2 O3 may be used a s an an ode material, the
some small quantity of Sb metal formation in the pro uct. Increasing the quantity of CA in the
conversionstarting
reactio n between so diu m ion s a nd the oxide lea ds to a high irreversible cap acity loss
precursor increased the Sb metal and decreased the Sb2O3 content. Finally, the PXRD pattern
on the firsotf cthyecSleb ([S3b0Ac3:C 4A]. :OTxhis1:3m :2i)gph
rotdb uect ushnodweesdiroa nblylepuirne Sabfm ull
etacl e plrle,se
snot.additional optimization was
undertaken soTahes pto resoeb ntcae ionf caarpbuonrefrS om bp CA rordeduucctt.ioTnhgeivP esXaRbD roapdabtatenrdnatocfa.S2b5(3S0bA inc:PC XARD :O, sxhow1n:1 in:2) shows
some smalFl iqg uraen1tai,tybeocof m Sbingmm etoarle fiontremnsaetaiosnthienCtA hecopnrtoen dtuisctin
. cIrnecarseda.sHinogwtehveerq, iut asnhotiutly
d o bfe CnoA ted
inthth ate starting
precursor increased the Sb metal and decreased the Sb2 O3 content. Finally, the PXRD pattern of the Sb
(SbAc:CA:Ox1:3:2) product showed only pure Sb metal present.
The presence of carbon from CA reduction gives a broad band at ca. 2530 in PXRD, shown in
Figure 1a, becoming more intense as the CA content is increased. However, it should be noted that
the Sb metal in the Sb (SbAc:CA:Ox1:3:2) product exhibits broad, weak peaks in the PXRD pattern.
Batteries 2017, 3, 20 4 of 16

This Bm ay be indica tive of the small crystallite size present in the Sb particles, or the low crysta4 lolfin16ity of
atteries 2017, 3, 20
the sample.
tShienScb
em Sbetpalairntitchl e Ssbiz(eSbisAac:kCeAy:O faxc to1r:3a:2ff)epcrtoindgucittsexehleibcittrsobcrhoeamd,iw caelapk eprefaokrsminanthce ,PiX tR isDimpapttoerrtna.nt to
deterTm hisne mtahyisbe prin
iodrictaotisvuebosfetqhueesnmt atellsctirnygst.aSllcitaensnizine gpreelesecn
trtoin mtheicSrobspcaorptiycl(eSsE
, oMr )thwealsow cacrryiestdaloliuntitoyn the
Sb (SobfA thce:C
saAm:O plxe. 1:3:2) material, as shown in Figure 1b,c. Examination of these images showed the
presence of larg e parrttiicclleesiz(ue pistao,kaen
Sin c e Sb ydfaicnto clruadffiencgti,n1g00itsem lecin
trosciz
he)miincatlhp eeprfroordmuacnt.ceI,t iht aiss ipmrpevoriotaunstlytobeen
determ ine this prior to subsequent testing. Scanning electron microscopy (SEM) was carried out on
note that autoignition self-combustion reaction s can rea h high temperatur es, som etimes in excess of
the
C Sb (SbAc:CA:Ox1:3:2) material, as shown in Figure 1b,c. Examination of these images showed
1000 the [29]. Given that the melting point of Sb is ca. 630 C, and that of Sb2 O3 is Itca.
presence of large particles (up to, and including, 100 m in size) in the product.
656 C, it seems
has previously
likelybeenthatnoted
high thattemperatures were reached during the self-combustion
autoignition selfcombustion reactions can reach high temperatures, sometimes stage, leading to the product in
meltein xcgeassnodf a1g 00g0loCm[e2r9a]t. iG
ngiveto
n fthoarm
t thtehm eseeltlianrggpeoSinbt pofa rStbicilsecsa. . F6u
30rthCe,racnhdatrhaacttoefriSzba2O tio n of the par ticle
3 is ca. 656 C,
size it
w aseseu mnsdliekreta
lyktehna,t ahnig
dhthteemrpeesrualttusrpesrew s ereteredaicnheTdab dlueri1n.g the selfcombustion stage, leading to the
product melting and agglomerating to form these large Sb particles. Further characterization of the
Tarbtliecl1
p e.sM
izedwiaans v
uanldueerstaokf epna,ratincd
letshiezeredsiu
stlrtsibpurteio
senn(tD
ed90in
, DT5a0b,laen1d. D10) and volume mean diameter
(D[4,3]) of Sb (SbAc:CA:Ox1:3:2).
Table 1. Median values of particle size distribution (D90, D50, and D10) and volume mean diameter
(D[4,3]) of Sb (SbAc:CA:OxP
a1r:a3m
:2)e. ter Sb (SbAc:CA:Ox1:3:2)
ParameDte9r0 (m) Sb (S9b4A
.8c:C2A.3:Ox1:3:2)
D50 ( m) 0.7
39.094.8
D90 ( m) 2.3
D10 (m) 3.9 0.2
D50 (m) 39.0 0.7
D[4,3] (m) 47.2
D10 (m) 3.9 0.2
D[4,3] (m) 47.2
As can be seen from this, the obtained Sb (SbAc:CA:Ox1:3:2) material consisted predominantly
of large pAasrctiacnlebse. seItenisfrw om ortthhisn, tohteinogbttahinaetdsS ubch
(Sb laArcg:eCA pa:Ortxicle1s:3:a2r)empaoteorria
lyl csounistiestdedfoprreedleocmtrin
oacnhtelymical
testing, nd are particula rly susceptible to pulverization resulting from the large volume angiceasl they
o f lar ge p a rtic les . It is w orth n o tin g th at su ch l a r g e p ar ticle s a re p o orly s u ite d fo r e l e ctr oche m
incurtedstu
inrg
in, gancdycalriengp.arM ticourleao
rlvyesru
, ascnepetliebclterotode puw lvoeu rilzdatbioenlersesualtiblnegtofrom mittih geatleartghee vvoolu lumme echeaxnpgaenssion,
they incur during cycling. Moreover, an electrode would b e less able to mitigate the volume
leading to faster fading due to loss lectrical contact. Thus, from the perspective of their physical
expansion, leading to faster fading due to loss of electrical contact. Thus, from the perspective of their
properties, this material is not well suited for electrochemical testing.
physical properties, this material is not well suited for electrochemical testing.
Raman Raman spectroscopy
spectroscopy was was thenthencarried
carriedout out on on the the Sb Sb (SbAc:CA:Ox1:3:2)
(SbAc:CA:Ox1:3:2) material
material in order
in order to to
exameixnaemtihne S thbe aSnbdancdarcbaornbocnocnotn etnetnitningg rereaateterrddeettaaiill,, as sshhoowwnnininFF igiu
gruere2. 2.

F igure 2. Ram an spectra taken from the Sb ( c: CA:Ox1:3 :2 ) product and a Sb stand rd.
Figure 2. Ra man spectra taken from the Sb (SbAc:CA:Ox1:3:2) produ ct and a Sb standard.

It has previously been shown that the structure of Sb metal is trigonal A7, and that its Raman
sIp
t ehcatrsupmrecv
oinosuisstslyofbaenenEgsh anod
wA n1tghbaatntdh(ehstrreusceteunraetocfa.S1b12mcem ta1l aisndtr1ig5o0 ncaml1A),7w, h
an
icd
h cthorarteistpsoR
ndaman

specttroutmrancsovnesrissetsanodf alonnEgigtuadnidnaAlm1gob tiaonndw(ihtheirne tsheeen
strautccta
u.re1,1r2escpm 1
ectivaen lyd[3155]0. cm1 ), which correspond
to transveTrhsuesa, ansdclaonnbgeitsued eninfarol mo thteiosnpew ctirtu
hm
in, the Ssb tru(ScbtA
urce:C, A
re:sOpxe ct1iv
:3e:2ly
) p[3ro5d].uct contains Sb metal.
ITt h
isuw s,oarsthcann otb
inegsteheant, firnomcomthpeasripsoecntrtoumth,etS hbe sStban(dSabrA
dcs:p CeA ct:rO
ux m , t1h:e3:S2b) p(SrboAdcu:C
ctAc:o
Onxt
ai1n:3s :S2)bEmg etal.

ba n d is sm a ller t h a n th e A 1g band. This ma y be indicative of some sligh t deg ree o f structu ra l disorder
It is worth noting that, in comp arison to the Sb standard spectr um , the S b (SbA c:CA:Ox1 :3:2) Eg band
in the tr sverse direction , possibly due to the partially amorphous nature the Sb or to the short
is smaller th an the A1g band. This may be indicat ive of some slight degree of structural diso rder in the
Batteries 2017, 3, 20 5 of 16

transverse direction, possibly due to the partially amorphous nature of the Sb or to the short-ranged
crystBaaltlteirnieist2y01f7r,o3m
, 20 small crystallites, as seen by PXRD. However, further characterization w 5 oof u
16ld be
necessary to determine this. Also visible in the Raman spectrum are D and G bands, which may be
assocriaantgeeddwcirtyhstcaallribnoitny rfersoim dusemraelm l cariy nsintaglliateftse, ratshe sed en ecboymPpX oRsiD
ti.on Howtehveerc,itfruicrth aceirdcghealr.acte
Quraiznattiiifocnation
would be necessary to determine this. Also visible in the Raman spectru m are D a nd G bands, which
was u ndertaken and the amount of carb on res due was found to b ca. 35 wt %. W hile the presence of
may be associated with carbon residue remaining after the decomposition of the citric acid gel.
lar ge quantities of carbon in the product might be expected to help mitigate volume expansion, and
Quantification was undertaken and the amount of carbon residue was found to be ca. 35 wt %. While
thus the
increase cyclability, it would also necessarily significantly decrease the gravimetric capacity based
presence of large quantities of carbon in the product might be expected to help mitigate volume
on theexpto ansion,map
ta l c o nodsittheums aisnsc.reTahse lcoyw claIDbi/lIiGty,vaitluw e ofouu ldndalisno thnecR esasm
arailny sspigenctirfiucamntilnydd iceactreesastehethheighly
grapghriativcim sterturcictucraepaocfityhebacaserdboonn rtehseidtu otal composite mass. The low ID/IG value found inutshley R
e , w h ic h c o u l d b e a c o n s equ e n ce o f t he p re vi o maemnatnioned
highstpeem p e r at u r e s r a ch e d d u r i n g th e s e l f - co m b u s ti o n .
ctrum indicates the highly graphitic structure of the c arbon residue, which could be a consequence
oGf itv he prtehveiopurselsyem nceentoiof nseigdnhiig
fchatnetmqpuearanttuitrieessroeaf cchaerdbodn u,riansgw theellse
alsftchoemlbaurg steiopna. rticle size, it seems
unlikely G thivaet nthth eesepm resaetn
ecreiaolsf saigrenicfiucrarnetnqtulyanw titeilels-souf icta n,uas waesllabsatthteerla
erdboto yrgerapdareticp leusriezea, n ittism
eeo mnsy for
lab-sca research. H o wever, it should be not ed th at this synthe tic rou te nevertheless possessefsorsome
u n lik e ly th a t t h es e m a te ri a ls a re cu rr en tly w e ll su ite d to u se as ba tter y g ra d e p u r e an tim o n y

attralcatbiv
secaple
rorp
eseeratrie
chs,. H
suocw
heavsert,hiet srhaopuildditbye w
noi tedwthhaitcthhitshseysnyth
netthicesriosum
te anyevbeertchoeles
mpsleptoesd
se, stshees sre
olm
ateively
attractive properties, suc h as the rapidity with which th e synthesis may be completed, the relatively
low temperatures ne ded , the availability of reagents, and the lack of ha logenated precursors and
low temperatures needed, the availability of reagents, and the lack of halogenated precursors and
contaminants. Further optimization of this synthetic route may lead to a purer product with smaller
contaminants. Further optimization of this synthetic route may lead to a purer product with smaller
particle size,size,
particle which which would
would bebe better
bettersuited
suitedforforelectrochemical
electrochemical testing. testing.

2.2. Antimony Oxide

2.2. Antimony Synthetic
Oxide Route
Synthetic Route
In orId n eorrd toerhtaovheavgeregarteeartecrocnotnrtorlool of fth theetteemperatturreedduurirnin ggthtehe cocm ob mubstuiostnioonf tohfe tchitericciatrciicd a(C
ciAd)(CA)
gel, agnel,aaltneranltaetrinvaetirvoeurtoeuw te awsads edveivsiesd edwwhhicichh eelliiminatteeddtthheeuuseseofothtehe am amono iunm iunmitrnaitteraotxeidoizxiindgizing
agenatg. eAng t.aAing,atino, m
toam keakuesu e soeforferaedaidly
ilyaavvaailialabblle, chlorriiddeef-rfere chcehm em
icaiclsa,la
s,natin
mto imnyon oxyidoex, indietr, in
c iatcrid
c ,acid,
and caintdri citarciicdacwiderweeerm e epm lopyloeyded asatshtehestsatarrtitinngg rre agenttss.. IInnsumm
su mmarayr,yt,htihs issysnythnetshisesmisay
mbaeyth boeutghhotuogfht of
as taaksintagkin
plgacpelaocveeorvtew ro twsotesptesp: s(:i)(iG
)Gelealatitoionn, ,aanndd ((iii) Combbuusstitoionn
, a, sashsohw onwinn iSnchSecm h e 1.e 1.
StepS(tie)pG(ie)lG ateiloantioisn uisnudnedrteark
taeknenbybydd isissolv O precursor
lviinngg tthe Sb O3 precursoarnadncditrciictraiccid
2
acgiedllin
gegllaingg enatginent in
2 3
nitricniatrciicda, cfiodl,lo
followed by heating to form the gel. Continued heating, to ensure the maximum removal
wed by heat ing to for m the gel. tinued heat ing, to en sure th e m axi um removal
of liquid, is maintained until an orangebrown solid precursor is formed. This is then removed,
of liquid, is maintained until an orange-brown solid precursor is formed. This is then removed, loosely
loosely ground via pestle and mortar to form a powder, and transferred to a boat.
ground via pestle and mortar to form a powder, and transferred to a boat.
Step (ii) Combustion is undertaken by heating the precursor under a constant gas flow, at the
selected teCm
S t ( ii) opmeb
rautu
strieon
anid
su fonrdtehretaskee
lenctby h
ed tie
maet.inA
gfttehrecp
oorelicnugrsaonrd ugnrd
inedrinagc, otn
hesta
finalgp
arsolfdo
uwct, iast the
selecotebd t e
tained. m p erature and for the selected time. After cooling and grinding, the final product is obtained.

Scheme 1. Schematic diagram of solgel synthesis.

Scheme 1. Schematic diagram of sol-gel synthesis.
Examination of the starting Sb2O3 reagent was undertaken so as to identify its phase. As can be
sEex
en
amfrionm
attihoenPoXfRtD
hedsattaar, tsih
nogwSnb2inOF3igreuarege3n
, itt w
coanssiusn
tsdoefrptaukr en
sesnoaram
s oto
ntid
teeSnbti2O
fy3.its phase. As can be
seen from the PXRD data, shown in Figure 3, it consists of pure senarmontite Sb2 O3 .
Batteries 2017, 3, 20 6 of 16

Batteries 2017, 3, 20 6 of 16
TBh
atu
tersie,sw
20h
17i,le
3, 2th
0 e presence of senarmontite Sb2 O3 may result from either unreacted pre6co ufr1s6or or
insufficien Tthluyso
, w pthimileiz
theedprreeascetnicoenocf osn
endairtim
oonnst,ite eSbp2O
re3sm
enacyero
esfuvltalfe
ronm
tineiitheSrbu2nOre3 aacn
tedd Spbrem
cuertsaolr m
oray be
attribiu ffTitchoiu
ntseud s,tlw
etn h il e theizp
heyeof fp tim
resen c e o f senar mo n t,itteheSbp2rO
t ofetd her eanctvioirno cnomdeintitoen xs p
m
e riencees d
3 e caey
nd re s ult from eit her u nreacted prec
uroifnvg alseynntitn hiet siSsb. 2O 3 and Sb metal
umrsaoyr boer
insufficiently
attr ibuted to the optimized
effect ofreaction
the env conditions,
iro n mentthe e xpresence
perienced of valentinite
d uring s Sb2O3 and Sb metal may be
nitially,
Iattrib the synthesis was perfor ed at 300 C for 45 min. under a constant flow of argon gas.
yn thes ut e
Initia is.lly, the synthesis was performed at 300 C for 45 mins.yunntd
d t o th e e f fe ct o f t h e en vir o n m e nt e xp e r ie n ce d d u ri ng hesias.constant flow of argon gas.
The PXRD Inpattern
i tial l y, thof
e the
sy n product,
thes shown in Figure 4a, reveals that no Sb was present. Instead, ther e
The PXRD pat ern of product, sh wn in Figure 4a, reveals that ndoerSba w
is w a s p er for m e a t 3 0 0 C f o r 4 5 m in . un coansstparnetseflnotw
. Inosftaeragdo,nthgearse.
was ow n ly S b O i n b o t h se n a r m o n t i e a n d v a l e i t e f o r
Th e P X2RD3pattern of the pro du c t, sho w n i n Figure 4a, r evea ls that no Sb was present. Instead, m s .
there a s o n ly S2b 3O in b th senar m o n tite a n d v alentinite for ms.
was only Sb2O3 in both senarmontite and valentinite forms.

FigFuirgeur3e. 3P.XPR
XDRDpp
atatteterrnnooff tthe staarrttiinnggSSbb
2O3 material.
2O 3 material.
Figure 3. PXRD pattern of the starting Sb2 O3 material.

Figure 4. (a) PXRD patterns of materials synthesized with varying temperature, valentinite Sb2O3 is
Fiagrukreed4w
. (itah) P;XSR D pimattern s of:f (m at eri3a0ls0 s y nthes ized wi t ; (d,ey)iSnbg6t0e0mpCe .rature, valenti
Figurm
e 4 . (a) P X R*D p Ea M
tternasgeo sf omabte)rSiitb
aelSsb2sOy n Ct;h(ec)siSz be5d00wi C
3 is
th varyi ng tem perature, vale
ntinite Sb O is 2 3
marked with *; SEM images of: (b) Sb 300 C; (c) Sb 500 C; (d,e) Sb 600 C.
marked with *; SEM images of: (b) Sb 300 C; (c) Sb 500 C; (d,e) Sb 600 C.
Batteries 2017, 3, 20 7 of 16

SBuatbtesrieesq2u01e7n, 3t, 2s0yntheses at increasing plateau temperatures were undertaken to invest7ig ofa1t6e the
effect of the heating regime on the final product. The PXRD analyses of the resulting materials shows
that increaSsuib nsgeqth uenctaslcyinnta hteisoens taetminpcererastiunrge p dloateesaiundteem ep
deirnacturereassewtehre Subndceorntateken
nt itno tihnevefisntiaglatperothdeuct.
Exam ination of the particle size of th e prod ucts, shown in Figure 4bd, iisng
e ff e ct of th e h e at in g re g im e o n th e fin al p ro d u c t. Th e PX R D a na lys es of th e re su lt a lmsoatreerviaelas lsih nogw. sFrom
that increasing the calcination temperature does indeed increase the Sb content in the final product.
this it can be seen that increasing the calcination temperature not only results in a purer product, but
Examination of the particle size of the products, shown in Figure 4bd, is also revealing. From
also appears to increase the product particle size.
this it can be seen that increasing the calcination temperature not only results in a purer product, but
Tahlso appeyarb
i s m a s eto siingcnreia
fisceatnhte gprivod
enuct h peartpicrleevsiio zue.s observations regarding the particle size of the
SbAc:CA:T Ohxism 1:a3y:2b. eIf,siagsnsifuicgagnet sgteivde,nthth eeseplrfe-cvoiom usbuosbtsieorn
vaotfiotnhse rgeeglard
wiitnhg th
thee oppatritm
icliezesd izeCA of:Othxeratio
is indSebeA dca:CcA hi:Oevxi ng 1:3h:2ig. Ihf, taesmsupgegreastuterde,st,htehsieslfw comlbdusbteioinnokf eth eepigneg
l wwitihththteheospetim
reiszued ltsC, Aw:O hxerreathioigher
tempeisrain tudreeedsyancthhievsiensghhaivgeh ltaerm geprerpaaturtriecsl,etshoisf w a opuulrderbeprinodkueecp t.inTghawtitbheitn
hgestehreescualstes, wcahrerfeulhcigohnetr ol of
tempeterm atp uerreaw turilel sbyenk theeysetso hm avineilmarigzein
rg paprtia rctliecsleofsiazpeu . rer product. That being the case, careful control
Ionf te
a nmepfefroartturteo w reild
l bueceketyhteo cm alin
c imaiztiionn g ptearm ticle
p saiztu e.re, slightly reducing gas (5% H /argon) was
2
used. Com Inpanriesfofo
nrb
t teotw
reedeunceth
theePcal
XR ciD
nap
tio
antteterm
nspeorfatth
ueret,w
sliogh
mtlaytererd
iaulcsinsygngtahse(s5i%
zeH
d2/aatrg5o0n0)w
Ca,sounseedu.nder
Comparison between the PXRD patterns of the two materials synthesized at 500 C, one under an
an ar gon and one under an H2 /argon gas flow, reveals that the product formed under an H2 /argon
argon and one under an H2/argon gas flow, reveals that the product formed under an H2/argon has
has decreased Sb O content, as shown in Figure 5a.
decreased Sb22O33content, as shown in Figure 5a.

FigureFigure
5. (a)5.PXRD
(a) PXRD patterns of materials synthesized under argon and H2/argon continuous gas flow;
patterns of materials synthesized under argon and H2 /argon continuous gas flow;
SEM images of (b) Sb 500 C (argon) and (c) Sb 500 C (H2/argon).
SEM images of (b) Sb 500 C (argon) and (c) Sb 500 C (H2 /argon).
Given the increasing reduction of Sb2O3 under H2/argon, it was decided that the use of this gas
Gmiavyenweth ll efaicnilcitraetaeslionwgeretdem ucpteiroantuoref rSeba2cO tio3nus.nHdoew r eH
ve2r/, arcgoomnp, airtisw
onasbedtewceid
ened
SEtM haitmtahgeesutsaekeonf this
gas moafythw e etlwl ofam cialitteartiealslo,wsheorwtnem inpFeirgautruere 5br,eca, cretivoenasls. tH
haotwth eeveSrb, a50c0omCp(arigsoonn) bhaestw
a eneonnSuEnMifoirmages
2/argon) m ateri
taken of the two materials, shown in Figu re 5b,c, reveals that the Sb 500 C (argon) has a nonr-m
di strib u tio n of sm a lle r p a rticl es , w h il e the Sb 50 0 C (H a l a pp ea rs to h a ve fo uendiform
aggl erations of more uniform, small particles. Nevertheless, it would seem that the use of 5%
distribution of smaller particles, wh ile the Sb 500 C (H 2/argon) material appears to ha ve formed
agglomerations of more uniform, small particles. Nevertheless, it would seem that the use of 5%
Batteries 2017, 3, 20 8 of 16
Batteries 2017, 3, 20 8 of 16

H2 /arHg2o/anrgons w gailsl b
weilal ubeseafuulsteofo
ull ftooroflafcoirlitfaciin
litgactihnegmcihceam
l riceadlurcetdiounctiaonndatnhde ftohremfoartm ioantioofnSo bf. ISnb.gIenneral,
in addgietnio
ernalt,oinhe
ad atdiintigontetm
opheartain tugrtee,mhpeeartaintugret,im
heeatm inagytiamlseomhaayvaelsaoshigan veifiaca
singtne ffetcht eon tthuere of a
iffifceacntt oen
nature of a product. To examine this, a comparison was made between Sb heated under the
product. To examine this, a comparison w as made be tw een Sb heated under the conventional regime
conventional regime (45 min at 500 C under H 2/argon) and Sb heated under the same conditions
(45 min at 500 C under H2 /argon) and Sb heated under the same conditions except for the heating
except for the heating time (which was increased to 100 min). Subsequently, the PXRD patterns
time (which was increased to 100 min). Subsequently, the PXRD patterns shown in Figure 6a.
shown in Figure 6a.

Figure 6. (a) PXRD patterns of synthesized materials heated under H2/argon at 500 C for varying
Figure 6. (a) PXRD patterns of synthesized materials heated under H2 /argon at 500 C for varying
times; SEM images of (b) Sb 500 C (H2/argon) 45 min and (c) Sb 500 C (H2/argon) 100 min.
times; SEM images of (b) Sb 500 C (H2 /argon) 45 min and (c) Sb 500 C (H2 /argon) 100 min.
From the SEM images, shown in Figure 6b, it can be seen that the two samples share similarities,
Fw roitm
h tbhoethSEcM onsiimstainggeso, fshsomwalnl ipnarFtig cluerse f6ubse, d
it ctoagneb theesr ee
ton fto hram
t thlaergtw eroasgagm lopmleesrasth
edarepasrim ticilleasr. ities,
with bHooth wecv oenrs, iisttm
inagyoaflssombaellsepeanrttihcalet sthfius sdeedgrteoegoefthaegrglto foermtiolanrigsegrraeagtgelroam ft era1t0e0dmpia nrtthicalnesa.ftHero4w 5 ever,
min. Thus, while the increased heating time does indeed imp ve the product purity, care must be
it may also b e seen that this degree of a gglom eration is greater after 100 min th an after 45 min . Thus,
taken to optimize this as it may also effect the product particle size.
while the increased heating time does indeed improve the product purity, care must be taken to
To summarize: it would appear that (A) decreasing heating temperature decreases particle size,
optimize this as it may also effect the product particle size.
but increases Sb2O3 impurity; and (B) increasing heating time decreases Sb2O3 impurities.
To suTm hmusa , riitzwe:aist pwr ouold sedaptpheatarde thcraeta(sAin)gdtehcerehaesaitinngghtem atpinerag teure
m pbeurtatinucrreeadseincrgeathsestip maertm icaley size,
but inrcerseualst ein
s Sabn2SOb3pirm odpuucrtitw
yi;tahnddec(rBe)aisn edcrp earstiincg
le hsiezaet.in
Tghetifm
irset d meactreeraiaslew
s Sasb2sO yn3th im
espizuerditbieysu . sing a
Tdheucrse, aist ew
d atsep mrpoeproastuerde th
coamt dpeacrraetiavseintgo thSbe h5e0a0tin C g t(eHm2/paergraotnu) re10b0utmin inc,rebaustinkgeteh peintgimaell moathyeresult
in an p Sb arp amroedteurcstth weitsham decTrehaesreedsupltairntgicplerosdizuec.t,TShbe4i6f 0rstCm(H at2e/arrigalonw) a1s00symnitnh, ewsiazsetdhebnyaunsailnyzgead duesicnrgeased
tempePrX aR tuDre, acsosm hopw orSeb7a5.00 C (H2 /argon) 100 min, but keeping all other parameters the same.
arnaitnivFeigtu
The resulting product, Sb 460 C (H2 /argon) 100 min, was then analyzed using PXRD, as shown
in Figure 7a.
Batteries 2017, 3, 20 9 of 16
Batteries 2017, 3, 20 9 of 16

Figure 7. (a) PXRD patterns of materials synthesized with antimony oxide (Sb) and citric acid (CA), Figure 7.
(a) PXRD patterns of materials synthesized with antimony oxide (Sb) and citric acid (CA), heated
under H2/argon at 460 C for varying times; SEM images of (b,d) Sb 460 C (H2/argon) 165 min;
heated under H2 /argon at 460 C for varying times; SEM images of (b,d) Sb 460 C (H 2 /argon) 165 min;
and (c,e) Sb 500 C (H2/argon) 100 min.
and (c,e) Sb 500 C (H2 /argon) 100 min.
From this, it can be seen that reducing the temperature but maintaining the same heating time
Freosm
ulttshin
s, aitncianncrbeeasseeienn Stbh2aOt3reim
dp uucrinity
g. tIhnecrteeam
sin
pgertahteurheeabtu
intgm tiam
ine,tahionw
inegvetrh, edsoaem
s reed huecaetinthge time
resultsquin
anatin
tyin
ofcrSeba2O se3 iim
n pSubritO
2 3
y, leimadp inugrittoy.thIenScbre4a6s0inC
g (H
t he2/argon) 165
h e a t i n g tim ien, p
hroow
duecvt,erw , hdicohescornetdau
incse the
nearly pure Sb.
quantity o f Sb 2 O3 impurity, leading to the Sb 460 C (H 2/argon) 165 min product, which contains
Using SEM, it is possible to compare the particle size of the Sb 460 C (H2/argon) 165 min product
nearly pure Sb.
and the Sb 500 C (H2/argon) 100 min sample, as shown in Figure 7be. This reveals that while both
Um C (H /arg on) 165 min product
siantgerSiaElsMc,ointsiisstpoofsfsuibseled taogcgolommpeararetetshoef psamratilcl lpeasritziceleosf, tbhyecSobm4p6a0riso n the2 Sb 460 C (H2/argon)

and th1e6S5 bm5i0n0prC oduct p rticles seems les fused a nd more dispersed. This woT
( H 2 / a r g o n ) 1 0 0 m i n sa m p le , a s s h o w n i n F i g u re 7 b e. ulhdisserevetaolsdtehm
aot nwsthrailtee both
materials consist of fused agglomerates of small particles, by comparison the Sb 460 C (H2 /argon)
165 min product particles seems less fused and more dispersed. This would seem to demonstrate that,
although further work would be necessary to truly obtain much smaller particles, the strategy being
employed here was successful in leading to a product with more desirable physical properties.
Batteries 2017, 3, 20 10 of 16

Batteries 2017, 3, 20 10 of 16

tFhuart,th
aletrhocu
hgahrafcutretrhiezraw
ti orkow
f o
pualrdtib
cleenseiczeessw
arays tu
ontd
ruelrytaok
betaninan
mdu,cahsssm
haolw
lernpia
nrtTicalbelse, t2h,eitstw
raatesgfyound

that ablelin
vgaleum
esploofyp
edarhtiecrleewdai s sruibcucetsio
sfnulwinerleasdm
inagllteorafoprrotd
hue cSt bw4it6h0m C
ore(H
d2e/
siararg
bloenp)h1y6s5icm
al ipnro
sapm
erp
tieles.than

for the SbF5u0rt0herCc(hH / a r g o n ) 1 0 0 m i n s a m p l .
ar2acterization of particle size was undertaken and, as shown in Table 2, it was found
that all values of particle distribution were smaller for the Sb 460 C (H2/argon) 165 min sample than
fToarbtlhee2S. bM5e0d0iaC
n v(H
al2u/a
ersgoofnp)a1r0ti0clm
e isnizsead
mip
stlrei.bution (D90, D50, and D10) and volume mean diameter
(D[4,3]) of Sb 460 C (H2 /argon) 165 min and Sb 500 C (H2 /argon) 100 min.

Table 2. Median values of particle size distribution (D90, D50, and D10) and volume mean diameter
(D[4,3P])aorambe4t6e0r C (H2/Sarbgo4n6)016C
fS 5m in2 /aanrdgoSb
(H n )510065Cm(iH S)b1500 miC
n2/argon n. (H2 /argon) 100 min

D
P9a0ra(m
me)ter Sb 460 C (H122./0argo0n.5) 165 min Sb 500 C (H12/9a.5rg
on1).6100 min
DD
5090((
mm) ) 124..020.05.1 19.5.9 1.60.2
D10 (m) 1.0 0.1 1.5 0.1
D50 (m) 4.2 0.1 5.9 0.2
D[4,3] (m) 5.6 8.5
D10 (m) 1.0 0.1 1.5 0.1
D[4,3] (m) 5.6 8.5
This confirmed what was observed in the SEM images and expected from the synthesis
conditionTsh
is i.ceo.,nftihrm
ated
thewS
hb 60as C
at 4w obs(H
erv ed in th e SEM images and expected from the sy nthesis
2 /argon) 165 mi n product consis ed of smaller, less fused,
morecodnisdpiteirosnesdpi.aer.,titchlaetst, hm
e aSk
bi4
n6g0itCbe(H
tte2/rarsguoin
te)d16to
5 miintip
graotidnugctvcoolnusm
isetecdhoafnsgm
eas lalenr,dl,etshsufus,sebde,ttm
erorseuited
disp er s ed par ti cl es, m a king it b
for use as an anode m aterial in sodiu m io n batteries.et ter su it ed to m itiga ting volume changes and, thus, better suited for
use as an anode material in sodium ion batteries.
In order to further investigate the properties of these two materials, the Raman spectra of both
In order to further investigate the properties of these two materials, the Raman spectra of both
were were
collected and normalized using the A band, as shown in Figure 8.
collected and normalized using the A1g1g band, as shown in Figure 8.

FiguFreig8u.reR8a.m
Ram
n asnpesp
ctercatratatkaeken
n frfro
om C(H
m tthhe Sb 446600C (H2/argon) 165 min and Sb 500 C (H2
/argon) 100
2/argon) 165 min and Sb 500 C (H 2/argon)
m i n p r o s, a n d fr o m a
100 min products, and from a Sb standard. Sb sta n d a rd .

From the Raman spectra taken of the Sb 460 C (H2/argon) 165 min and Sb 500 C (H2/argon) 100

mFrionm pro thdeucRtsam thearne sapreecsetrvaertakneonteowf oth rtehySb fea4t6u0resC . (H2 /argon) 165 min and Sb 500 C (H2 /argon)
100 min pFriorsdtluyc, ttshethbearnedasraessiegvneerdaltonA ot1eg w
anodrtEhgyarfeaptruersesn.t, demonstrating the presence of antimony at
tFhiersntelya,rtshuerfbaacn ed osf tahsesp
igrnod ucttopA
ed ar1tgicalensd
. TEhge a Ergebapnredsoefntth, edtew moom nasteraritainlsgistheaesiply revsiesn
ibcle ,oin
f acnon titm
raostny at
the near-surface of the p roduct p ar ticles. The Eg band of the tw o m aterials is easily visible, in conetrast
t o th e S b ( S bA c:C A :O x 1 :3 :2) p ro d u c t w h i ch is lik ely du e to th e m o r e c ry t a ll in e n atu re o f th e s
to thperS odbu(cStsb A wch:iC chAm :Oay x be1i:n3f:e2r)repdrofrdou
mctthw ehPiXcR hDisplaitkt eln ys.due to the more crystalline nature of these
products Sw econdly, ther is no easily discernab le pattern that may be associated with Sb2O3. This would
hich m ay b e inferred from the PXRD patterns.
b e in keeping with the expected r uction mechanismi.e., that the reduction of the materials is
Secondly, there is no easily discernable pattern that may be associated with Sb 2O 3. This would
likely taking place due to reductive gases reacting with the product particles predominately at the
be inparticle
keeping with the expected reduction mechanismi.e., that the reduction of the materials is
surface.
likely takTin higrdply la, cDe adnudeGtobarnedu, catsisvigengeadsteoscraerb aoctninregsiwduitehotrh igeinparto indgufcro tm patrhteicclietrsicparceidohm ydinroactaerlbyoant the
partigcleel, saurerfsaticlel .present, though greatly decreased in intensity comparative to the Sb (SbAc:CA:Ox1:3:2)
pTrhoidrduclyt., T Dhiasnw doGuld baimndpsly, athssaitgtn
heodugth o ccaarrbboonnreresisdidueueis osrtiilgl ipnraetsienngt, firtoisminthfaer clietsrsicanacaimd ohuyndt rtohcaanrbon
gel, are still present, though greatly decreased in intensity comparative to the Sb (SbAc:CA:Ox1:3:2)
product. This would imply that though carbon residue is still present, it is in far less an amount than
in the acetate-based synthesis. The carbon contents of the Sb 460 C (H2 /argon) 165 min and Sb 500 C
Batteries 2017, 3, 20 11 of 16
Batteries 2017, 3, 20 11 of 16

in the acetatebased synthesis. The carbon contents of the Sb 460 C (H /argon) 165 min and Sb
(H 2 /argon) 100 min products were quantified by elemental analysis and2 found to be 14 wt % and
500 C (H2/argon) 100 min products were quantified by elemental analysis and found to be 14 wt %
12 wtand
%, 12
respectively.
wt %, respectively.
2.3. Electrochemical Characterization
2.3. Electrochemical Characterization
To inTvoeisntivgeastteigtahte tehle etlreocctrhoecm strisytroyf otfhtehSe bSb464060 CC((H
heim H22/arrggoonn) )161565mm
inin 0 (H
anadnSdbS5b0050C C2(/aHr2g/ ar) gon)
on
100 m1i0n0 pmro du c ts , c o i n c e l ls w e re f a b ri c a te d a n d c ycl e d
in pr oducts, coin cells were fabricated a nd cyc ledfirst w ith a single C/10 preconditioningcycle,
first w it h a si ng le C /1 0 p re c o nd iti o n i n g
then caytcvle, ty
ar hienngaCt v-raartyein
s goCr 1rCat,eassosrh1oCw , ans isnhoFwignuirne F9iag,ubr.e 9a,b.

FigurFeig9u. r(ea)9.R(aat)eRcaatp
e acbaipliatbyilp
itlyotpslo
atnsda(nbd) (cby)cclaybclialibtiylip neant a1tC1fCorfoSrbS4b64060CC(H(H
tyloptlsottas ktaek 2/argon) 1
2 /argon) 165 min
m in a nd Sb 500 C (H 2 /a rg o n ) 10 0 m in p
and Sb 500 C (H 2/argon) 100 min products. 1C is taken as 660 m A g . r o d u c ts. 1 C is ta k en a s 660 mA g 1
1 .

The rate capability plots, shown in Figure 9a, demonstrate that the Sb 460 C (H2/argon) 165 min
Thaeteraiatleecxahpibaibtsilit
m beyttp erlostpse, csihfiocwchnairn geFaigtuthre h 9iag,hdeer mraotensotfr4aC
te(tchaa. t11th5 eanSdb 84560mACh(gH12f/oarrSgbon 46) 016
C5 min
mate(rH ia2l/aerxghoinb)i1ts65bm etitneran sp 1 Sb 460 C
deScbifi5c00ch Car(gHe2/aatrgthone )h1i0g0hm erinr,arteespoef c4tC
ive(lcya). w11 h5 anisdli8k5elm
ich ydAuhe g to theforsmaller,
(H2 /laersgsofn
u)se1d65pamrtiinclaen sd ofStbhi5s0m 0 atC er(iaHl 2b/eainrgobne)tt1e0r 0sumitiend, rto
estphecdtiivffeulsyi)owno hficshodisiulim
keiloynsdu
inetoto
, atnhde o sm
utaller,
less foufs, eth
depm aratiecrlieasl douf rtihnigs cmycaltienrgi.al being better suited to the diffusion of sodium ions into, and out of,
the material during cycling.
At the highest rate, 8C, both materials delivered similar low capacity, indicating that the
morphology of these materials, which is yet to be fully optimized, is not well-suited to sodiating and
 Batteries 2017, 3, 20 12 of 16

BatterieA
s 2t01t7h, e
3, 2h0ighest
rate, 8C, both materials delivered similar low capacity, indicating th1a2 toft1h6e
morphology of these materials, which is yet to be fully optimized, is not wellsuited to sodiating and
desodiating a t this high rate. When returning to the slow rate, C/2, both materials were able to recover
desodiating at this high rate. When returning to the slow rate, C /2, both materials were able to recover
their original specific charge values, although the Sb 460 C (H 2/argon) 165 min material exhibited
their original specifi c charge values, although the Sb 460 C (H2 /argon) 165 min material exhibited
better capacity retention.
retention. Examination
Examination ofof the
the voltage
voltage profiles
profiles of
of Sb
Sb460
460 C
C(H 2 /argon) 165 min at
(H/
better capacity 2 argon) 165 min at
different rates (shown in Figure 10) reveals the expected electrochemical behavior , with the plateaus
dif rent rates (shown in Figure 10) reveals th e expecte d electr ochemical behavio r, with the plateaus
decreasing at increasing rates, likely due to larger polarization .
decreasing at increasing ra tes, likely due to larger polar iza t ion.

FF
igig
uurere101.0V
.V s foSf bSb464060 CC(H
olotaltgaegeprporifolfeilseo (H2/2/aarrggoonn)) 116655 m
miinn ttaakkeennaattvvaarryyiinnggCC-rraatteess..

TThheepplalateteaauussooccuurraattvvooltlataggeessccoom mppaarraabbleleto toth thoosseerreeppoorrteteddin

inth theeliltite
erraatu
turree, ,ddeemmoonnsstrtraatitn
inggththee
electro chemical behavior of this material is in keeping with that which may be reasonably anticipateedd..
e le ct ro ch em i ca l b e h a v io r o f th is m ate r ial is in k e e p i ng w i th th a t w h ic h a y b e r e as o n a b l y a n tic ip a t
The 1st cycle sodiation valuesca. 803 and 762 mAh g1 for Sb 460 C (H2/argon) 165 min and
The 1st cycle sodiation value sca. 8 03 and 762 mAh g1 for Sb 460 C (H2 /argon) 165 min and
Sb 5 0 C (H2/ 10 in, respectively of both materials taken at the C/10 rate are shown in
Sb 500 C (H2 /argon) 100 min, respectivelyof both materials taken at the C/10 rate are shown in
Figure 9b , where it can be s n tha t they are greater than the theoretica l capacity o f these materials
Figure 9b, where it can be seen that they are greater than the theoretical capacity of these materials
( 0 mAh g1 1). t I for ation and other side reactions. The 1st cycle desodiation
(6 60 mAh g ). This is likely due to SEI formation and other side reactions. The 1st cycle desodiatio n
values are ca . 472 and 4 mAh g 1
1 ti cal capacity, likely due to A) unoptimized
values are ca . 472 and 444 mAh g , lower than the theoretical capacity, likely due to A) unoptimized
particle size and B) electrochemica ly inactive residual carbon in the product adding to the product
particle size and B) electroche mically inactive residual carbon in the product adding to the product
mass . il better rate capability has been previously reported when graphene is used to from
mass. While better rate capability has been previously reported when graphene is used to from
composites [30 3], in tial desodiation capacities at low ra tes are generally reported in the range of
composites [30333], initial d esodiation cap acities at low rates are generally reported in the range of 450
450 to 500 mAsimilar h g1similar to our to findings. In some In
our findings. cases,
some thecases,
specific thecharge
specific reported
chargehere are similar,
reported here or are
to 500 mAh g1
x
similar, or ev en superior, to the literature. For exam e, SbOx nanoplates encapsulated by carbon
even superior, to the literature. For example, SbO nanoplates encapsulated by carbon lfakes prepared
flakes prepared f m SbCl3 in a threestep procedur [34] exhibited over 100 m Ah g1 at 4 A g1 (ca.
from SbCl 3 in a three-step procedure [34] exhibited over 100 mAh g1 1 at 4 A g1 (ca. 6C), while our
6C), while our onepot synthesis material delivered ab1out 115 mAh g at 4 C . T he specific charge of
one-pot synt1hesis material delivered about 115 mAh g at 4C1. The specific c1harge of 260 mAh g1 at
260eported
mAh g her at 1C report d here also exceedst1heat205 mAh g at 800 mA
800 mA g1 (ca. 1.2C) demonstrated g (ca. 1.2C) demonstrated
by Wang et
1C r e als o exceeds the 205 m Ah g
b y W a n g e t al . [ 3 3] fo r g r a p h e n e anch o re d S b / S b O x nanopart cles prepared via a twostep wet
al. [33] for graphene anchored Sb/SbO x nanoparticles p repared via a two-step wet chemical process
chemical process (involvin g the reduction of SbCl3 with NaBH4 in benzyl alcohol).
(involving th e reduction of SbCl 3 with N aBH 4 in be nzyl alcohol).
FFro
rommthth eecycy clcalb
aiblitliytyplpoltosthsohw
ow nn ininFigFig
u rue r9eb9, bit, m
it amyabye bseesneeth natthtahteth
caepcaacpitaycirteyternettieonntiaotn1Cat o1fCSbof
Sb 4 60 C (H2/argon) 165 m n is superior (ca. 50% and 38% for Sb 460 C (H2/argon) 165 min and Sb
460 C (H 2/argon) 165 min is su perior (ca. 50% and 38% for Sb 460 C (H 2/argon) 165 min and Sb
500 C (H2/ l , ic ay be attributed to the smaller, less fused particles
500 C (H 2 / argon) 100 min, respectively), which may be attributed to the smaller, less fused particles
being better able to mitigate the large volum e changes occurring during sodiation/desodiation . The
bein g better able to mitigate the large vo lum e changes occurring during sodiation/desodiation. The
overall capacity fading may be attributed, at least in the m ain, to pulverization resulting from the
overall capacity fading may be attributed, at lea st in the main, to pulverization resultin g from the large
large volume cha g s undergon by the antimony particles during sodiation/desodiation
volum e chang es und ergone by the antimony particles during sodiatio n/desodiation
The differential capacity plots of cycles 1 and 2 of Sb 460 C (H2/argon) 165 min, taken at 1C, are
The differential capacity plots of cycles 1 and 2 of Sb 460 C (H 2/argon) 165 min, taken at 1C, are
shown in Figure 1 .
shown in Figure 11.
Batteries 2017, 3, 20 13 of 16
Batteries 2017, 3, 20 13 of 16

FiFgiu
gruere111.1D
.Diffieffreernetnia ityplpoltostsofoSf bSb46
tilacl acpaapcaicty 4600CC((H
H22/a
/ragrgoonn))116655 min,, ccyycclleess 11 aanndd 22,, ttaakkeennaat t1C
1C. .

During sodiation, electrochemical activity is observed at ca. 0.47 V vs. Na++/Na during cycle 1,
During sodiation, electrochemical activity is observed at ca. 0.47 V vs. Na /Na during cycle 1,
and at 0.6 and 0.45 vs. Na+/Na during cycle 2. During desodiation, electrochemical activity is observed
and at 0.6 and 0.45 vs. Na+ /Na during cycle 2. During desodiation, electrochemical activity is observed
at ca. 0.78 V and 0.88 vs. Na+/Na during cycle 1, and in the 0.809 V vs. Na+/Na during cycle 2. These
at ca. 0.78 V and 0.88 vs. Na + /Na during cycle 1, and in the 0.809 V vs. Na+ /Na during cycle 2.
results are in keeping with those previously reported in the literature [36], implying that the
These results are in keeping with those previously reported in the literature [36], implying that the
sodiation/desodiation mechanism is generally consistent with the reversible alloying reaction
sodiation/desodiation mechanism is generally consistent with the reversible alloying reaction expected
expected for a material predominantly consisting of Sb.
for a material predominantly consisting of Sb.

3. Conclusions
This work examines sol-gel synthetic routes to producing Sb metal particles for use as anode
materials in sodium-ion batteries. Whiillee ffuurrtthheerr worrkk wou ulldd be necessary to fully optimize this
technique, particularly towards a smaller particle size, severrall key parametteerrss havee been found,,
l r l ,
including: heating temperature; heating time;; and choiice off gass lfl f oow..
By employing an understand ing of th e effect of th ese param eta
e m p lo y in g an u n d e r s t an d in g o f t h ef f e ct o f th es e p ersa,m itehtearssb, eietnhpaosssbib eelentopu on ssdiebrlteakto
e
u
some in itial optim ization. This has re sulted in the reduction o f particle size from large, 1la0r0ge,
n d tak e s o m e in tia l p ti m iz at io n. T h is h as re s u lte d in h e red u ctio n of p a rt icl e s i z e fr om m
10
p a0rti clmes ptoarticl
6e0s to m fu6s0edm aggfu losmederaagtegsloom f esrm ataelsleor fpsam rtaicllers. pT art
h eicolepst.imThizeatoip ontim ofiztahteiosne pofh ytshiecsael
parameters has been accomp anied by an improvement to the electrochemical properties, leadrin
hy sic a l p a r et s h a s b ee a cc o m p an ied b y an im p r o v e m e n t to th e e le ct r o c h e m i ca l p ope
g trotitehse,
Slebad46in0g Cto (tHhe/Sabrg4o6n 0 )1C65(Hm2/ianrg moant)er1i6a5l m whinicm h hataesriaanl w inh itiicahl dheassoadniaitnioitniacl adpeascoid tyiaotifocna.c4 a7p2acm itA
y hofgca1.
2
4 72 m A h g 1 and 50% retention over 60 cycles.
a n d 50% r etention over 60 cycles.
By further oop pttiimizzaattiioonn ooffth t heeppaara r am meetetersr,s,an ad ndofo fhe haetain
tigngtetm empepreartautruera enadnd tim time ien ip naprtairctuiclaurl,airt,
imt mayaybebp e opsossib silbeletotoim im prporvoevethtihsispro p ro cecsesssstsitlilllfu
furtrhtheer,r,leleaaddin inggttooSSbb ppaarrttiicclleess witthh iimprroved physical
and electrochemical charact eristics . Finally, it is wo rth nontginthe
e c tr h e c a l c h a r a cte r is ti c s . Fi n a lly , i t is w o r th n o ti g thpeotpeo ntteianltiuatlilit
utyilo itfyth oifstwhiosrk w toorklatbo
slacb
a-lescareleseraersceharocn h oi n einrm teremtaelltiacllaicnoad noe dm e am teartiearlsia lsn amnaem lyeltyhath t aat afafsatstan an ddfa facciliele ssyynntthheettiicc rrouttee to
antimony particles with moderate electrochemical performance has been devellooppeedd..
i t l tr c e i ca l p e rf o r an c e h as b e en d e v e

4. Materials and Methods

4.1. Synthetic Methods

The antimony acetate syntthetiic rroouttee waass aass ffoolllloow wss:: cciittrriicc aacciidd((CC66H88 O7,, 9999%,, Sigmaa Aldriich)),,
antimony acceettaattee ((SSbb((C
CH33CO2)22,,9999..9999%,, SSiiggma Aldrri ch)), and ammonium nitrate (NH44 NO3,, 9999..999999%,,
Acros Organics) oxidizing agent were dissolved in glacial acetic acid (40 mL) in the molar ratios
described ((bbaasseedd oonn00.0.0004422mm
ool lan
atnitm on
im oynyacaecteataet)e. )T. hT
ishsio
s lsuotliuon tiownaw s haesahteedatuen
dtiul nthtiel athce iaccaetciicdahcaid
boiled off, with the resulting solid being collected and ground to a powder. This powder was then
heated at 5 C min1 to 240 C for 15 min, under argon gas, to initiate the autoignition selfcombustion
Batteries 2017, 3, 20 14 of 16

had boiled off, with the resulting solid being collected and ground to a powder. This powder
was then heated at 5 C min1 to 240 C for 15 min, under argon gas, to initiate the autoignition
self-combustion reaction between the nitrate salt and citric acid-based hydrocarbon gel. After cooling
to room temperature, the resulting product was collected for characterization.
The antimony oxide synthetic route was as follows: antimony oxide (Sb2 O3 , 0.5 g, 5 m 99%,
Sigma Aldrich) and citric acid (C6 H8 O7 , 1.598 g, 99%, Sigma Aldrich) were dissolved in nitric acid
(HNO3 , 6870%). The solution was heated to 140 C to boil off the acid (which was trapped using
a condenser, to prevent noxious fumes). This precursor product was then collected, ground, and
heated at 10 C min1 , under the selected gases, for the selected temperatures and times (as detailed
in the results section).

4.2. Physcial and Chemical Characterisation

Powder X-ray diffraction patterns were collected on a Bruker Discover D8 diffractometer operating
in reflection mode with CuK1 radiation ( = 1.5405). Scanning electron microscopy images were
collected on a FEI Quanta 250 scanning electron microscope. A Raman microscope (Renishaw inVia)
using a 532 nm wavelength laser was focused through a microscope (Leica) via a 50x objective (Leica).
Particle size distributions were analyzed using a Mastersizer 3000 (Malvern Instruments) with a Hydro
MV. Elemental analysis was carried out using a CHNS Eager 300 elemental analyzer.

4.3. Electrochemical Characterisation

Sodium and lithium electrolytes were prepared from 1 molar sodium perchlorate (NaClO4 ) in
dried, distilled 1:1 wt % ratio ethylene carbonate:propylene carbonate, with 5 wt % fluoroethylene
carbonate (FEC) additive to improve cycling stability [18,19]. To evaluate the performance of the
antimony particles, composite electrodes were fabricated by casting an aqueous mixture (antimony
active material:carbon black (Super C65, IMERYS Graphite & Carbon):sodium carboxymethylcellulose
in a ratio of 75:15:10% by weight) onto a copper foil current collector. Coin cells were assembled
from CR2032 coin cell parts, the prepared antimony electrodes, a glass fiber separator (Whatman)
impregnated with the sodium electrolyte and a sodium (Na) metal counter electrode. In all cases, cells
were sealed in a glove box under air and moisture free conditions (O2 < 0.1 ppm; H2 O < 0.1 ppm).
The electrochemical measurements were performed at 25 C using a Maccor Series 4000 battery cycler.
All batteries were cycled in the 50 mV to 1.5 V potential range and the obtained capacities were
normalized by the total mass of composite material.

Acknowledgments: We acknowledge the financial support of the Ministerio de Economa y Competitividad

through the projects ENE2016-75242-R and the Juan de la Cierva grants (JLGC, IJCI-2014-20613). The authors
would also like to thank the Basque Government for financial support through ELKARTEK project CICE17.
We also gratefully acknowledge the support of Elena Gonzalo for her assistance with quantifying particle size,
Yan Zhang for the collection of Raman spectra, and Mara Juregui for collecting the PXRD patterns.
Author Contributions: N.E.D. and J.L.G.-C. conceived the initial experiment, N.E.D. carried out the syntheses,
J.L.G.-C. performed the electrochemical analyses, B.A. undertook the SEM characterization, all authors discussed
the results and contributed to the experimental design.
Conflicts of Interest: The authors declare no conflict of interest.

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