ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

ELECTRODEPOSITIONOFRAREEARTHMETALSINIONICLIQUIDS
E.BOURBOS1a, I.GIANNOPOULOU1,
I.PASPALIARIS1

A.KARANTONIS

D.PANIAS1b,

DepartmentofMiningandMetallurgicalEngineeringofNationalTechnicaluniversityofAthens,9,
IroonPolytechnioustr.15780ZografouCampus,Athens,Greece
2
Department of Chemical Engineering of National Technical university of Athens, 9, Iroon
Polytechnioustr.15780ZografouCampus,Athens,Greece
(a)ebourbos@metal.ntua.gr,(b)panias@metal.ntua.gr

Abstract
Inthispapertheavailableliteratureontheapplicationofionicliquidsinrareearthmetals
electrodeposition,isbrieflydiscussedandthemainelectrochemicalpropertiesofionicliquids,
in relation with such applications, are presented. In addition, the results of a preliminary
investigationforthesuitabilityofpyrrolidiniumbasedionicliquidsontheelectrodepositionof
lanthanumarepresented.
Introduction
Productionofrareearthmetalsandalloysareconventionallyperformedbyhightemperature
molten salts electrolysis, which creates highly corrosive environment and demands high
energy consumption. Recently, the use of organic solvents has been implemented for the
electrodepositionofrareearths;howevertheywereconsideredinadequate,duetotheirhigh
volatilityandtheirinflammability.
Ionicliquidsgainincreasingattentionintherecentyears,aselectrolytesfortherecoveryof
metalsmoreelectropositivethanhydrogen.Itconcernsforsaltsthataregenerallyliquidat
ambientconditions,consistingofabulkyorganiccationandasmallerorganicorinorganic
anion[1].Thevariety,thecombination,thepositionandthesizeofcationsandanionsadjust
remarkableproperties for ionic liquids, such as very low melting point, high chemical and
thermalstability,negligiblevapourpressure,abilitytodissolveawiderangeoforganicand
inorganiccompounds,importantionicconductivityandbroadelectrochemicalwindow[2].
These properties of ionic liquids, in combination with the nonflammability they present,
renderthemadvantageousfortheelectrodepositionofrareearthmetals,incomparisonwith
theorganicsolventscurrentlyused[35].
Preliminary studies have proven that ILs are capable solvents and electrolytes of reactive
metals, such as Li, Na, Al, Mg [68]. In this paper the applications of ionic liquids in the
electrodeposition of rare earth metals are reviewed and preliminary results of the
electrodepositionoflanthanumarepresented.
Electrodepositionofrareearthsinionicliquids
Theelectrodepositionofrareearthelementsfromionicliquidshasbeenmainlyinvestigated
withfourdifferentfamiliesofionicliquidsbasedontheircation.Itconcernsforimidazolium,
pyrrolidinium,ammoniumandthephosphoniumbasedionicliquidswithavarietyofanions.

PAGE|156

ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

Imidazoliumbasedionicliquids
It is the most widely investigated family of ionic liquids for metals electrodeposition.
Especially, the imidazolium chloroaluminate systems have been used successfully for the
electrodepositionofAlandrefractorymetalssuchasTa.
Inthecaseofreductionofrareearthmetalsfromimidazoliumbasedionicliquids,Tsudaet
al.[910]reportedthecodepositionofLawithAlfromaLaCl3saturatedEmimAlCl3system
with excess of LiCl and SOCl2 and not in pure EmimAlCl3. The lanthanum content of the
resultedAlLaalloywas0.05%upto0.50%,intermsofmassfraction.Inaddition,theco
depositionofLaCoalloyswasstudiedintheionicliquidBmimCF3SO3usingcoppercoilsas
cathodes [5]. Moreover, the codeposition of Sm and Co in BmimBF4 was reported [5],
throughinductiveeffectandthecontentofSminthefinalalloywasestimatedbetween5%
and40%.
Lin[11]etalin1993approachedtheelectrochemicalbehaviourofCe(III)/Ce(IV)coupleinthe
basic aluminium system (AlCl3 MeEtimCl) and via ultravioletvisible spectroscopy it was
stated that Ce(III) and Ce(IV) form complexes such as [CeCl6]x, whereas x=3 and 2
respectively.Jagadeeswaraetal.[12]researchedtheelectrochemistryofthesystemsCe(III),
Sm(III) and Eu(III)/Eu(II) in BmimCl. The application of cyclic voltammetry and
chronopotentiometryatplatinumworkingelectroderevealedthereductionoftrivalentCe
and Sm ions to the divalent state at various temperatures and found them to be quasi
reversiblereactions.In2006,Yamagataetal.[13]studiedtheelectrochemicalbehaviourof
redox reactions Sm(III)/Sm(II), Eu(III)/Eu(II) and Yb(III)/Yb(II) in the ionic liquid EmimTFSI
throughcyclicvoltammetryanditwasfoundtobequasireversibleorirreversible.

Pyrrolidiniumbasedionicliquids
Glukhovetal.[14]havestatedthereductionofY,GdandYbintheionicliquidBMPCF3SO3
onboth,platinumandcopperelectrodes.OnthevoltammetriccurvesperformedwiththePt
electrodesinthesystemsYandGdwiththisIL,theobservedcathodicpeakwithamaximum
valueof2.6V(rel.Ag/0.1MCl)wasattributedtothereductionofthetrivalentcationsto
themetallicstate.Theelectrodepositionofthesemetalswasperformedunderpotentiostatic
orgalvanostaticconditionsandatenuousblackprecipitatewasformedontheelectrodes
surface.ItwasalsoshownthatthereductionofYb(III)tothemetallicformoccursstepby
stepviaYb(II)formationandthelimitingstageofthecathodicprocessistheadsorptionof
themetalcationontheelectrode.Legeaietal.[15]haveshownthatthereductionofLain
OMPTFSIisanirreversiblereactionandthatLaelectrodepositioninthisionicliquidunder
potentiostaticpolarisationconditions1.5V(vsAg/AgCl),for120min,at298K,resultedin
thecathodicdepositofathickLafilmof350nm.
In addition, Yamagata et al. [13] studied by cyclic voltammetry the redox reactions of the
Sm(III)/Sm(II)coupleinBMPTFSIionicliquidusingaglassycarbonelectrodeanddetermined
theredoxreactionsasquasireversibleorirreversible.Theyalsostudiedtheelectrochemistry
ofYb(III)inBMPTFSIbycyclicvoltammetryandconcludedtoacathodicandananodicpeak
ataround0.95V(vsAg/Ag+),whichconsideredattributabletothereductionofYb(III)and
theoxidationofYb(II),respectively.TheelectrochemicalbehaviourofEu(III)inBMPTFSIwas
researched by Rao et al. [16] with glassy carbon and stainless steel electrodes, at various

PAGE|157

ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

temperatures.Thecyclicvoltammogramsrevealedaquasireversiblebehaviouroftheredox
coupleEu(III)/Eu(II)andanirreversiblebehaviourofthecoupleEu(II)/Eu(0),whichpresented
acathodicpeakattributedtothereductionofEu(II)tothemetallicstate.Inthesameionic
liquid (BMPTFSI) that contained also chloride anions, Hussey et al. [17] studied the
electrochemicalandspectroscopicbehaviourofNd(III)andPr(III).Accordingtotheirresults,
the electrolytic dissolution of both metals in this ionic liquids system produces only the
respective trivalent cations, which can be reduced to the Ln2+(II) state, but the resulting
divalent species exhibit only transient stability, undergoing rapid disproportionation to
Ln3+(III)andLn0states.

Ammoniumbasedionicliquids
Glukhovetal.[14]investigatedthereductionofY,Gd,YbintheionicliquidBu3MeNCF3SO3
andconcludedthatthedepositionoftheabovemetalsisonlypossibleonacoppersubstrate
anddoesnotoccuronaplatinumone.Bhattetal.[18]reportedthereductionofselected
lanthanidecations(La,SmandEu)tothezerovalentstateintheionicliquidMe3NBuTFSI.
ThelanthanidecationswereintroducedtotheionicliquidastheTFSIhydratecomplexes.
Cyclicvoltammogramsrevealedacathodicpeakat2.4VvsFc+/Fcforthelanthanumsystem
attributedtothereductiontometallicstate,whereastwopeakswereobservedforSmand
Eusystems,thelessnegativewereassociatedwith(III)/(II)reactionandthemorenegative
withthereductiontothemetallicstate.

Phosphoniumbasedionicliquids
In 2008 Matsumiya et al. [19] studied the electrochemical behaviour of Sm(III) in the
phosphoniumbasedionicliquids.ThediffusioncoefficientsofSm(III)weredeterminedvia
cyclicvoltammetry,chronoamperometry,chronopotentiometryandwereestimatedtobeon
the order of 108 cm2s1. It was stated that the trivalent samarium complexes in the
phosphoniumbasedionicliquidswereassumedtopresenthigherionmobilityinrespectto
thoseintheammoniumionicliquids,duetoweakerinteractionbetweenthecationandthe
anioninphosphoniumbasedILs.Inaddition,Kondoetal.[20]researchedthesuitabilityof
P[225]TFSIfortheelectrodepositionofneodymium.ThediffusioncoefficientofNd(III)was
investigated by chronopotentiometry with cylindrically symmetrical diffusion and was
estimatedontheorderof1011 m2s1at100 oC.ThecyclicvoltammogramsofNd(III)/P[225]
TFSIcontaining0.5moldm3NdTFSI3presentedananodicandacathodicpeakcurrentsthat
wereattributedtotheoxidationandthereductionofNd(III),respectively.Thereductionof
Ndcationwasobservedat2.5Vvsaplatinumwireimmersedinthesolutionusedasaquasi
reference electrode, compensated for the Fc+/Fc redox couple. The electrodeposition of
neodymiuminthespecificionicliquidwasperformedbypotentiostaticelectrolysisat3.1V
vsFc+/Fcat150oC.Ablackelectrodepositwasfineandformeduniformlyneodymiumparticle
andwasobservedbySEMandidentifiedfromtheevaluationofEDX.
Moreover, the electrochemical behaviour and electrodeposition of dysprosium (Dy) in the
phosphoniumbasedionicliquidP[225]TFSIwereinvestigatedbyKurachietal.[21].Thecyclic
voltammetricmeasurementsresultedinonestepreductionofthetrivalentdysprosiumion
in phosphoniumbased ionic liquid. On the other hand, no anodic peak ascribed to the
oxidation of dysprosium metal was observed in this electroanalytical study. The diffusion

PAGE|158

ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

coefficientandtheactivationenergyfordiffusionofthetrivalentDycomplexinthisILwere
alsoestimated,usingsemiintegralanalysis.ThediffusioncoefficientofDy(III)wascalculated
tobe2.01012m2s1at25oC,closedtothatofthetrivalentlanthanoidionsuchasEu(III)and
Sm(III)inphosphoniumbasedionicliquids.Inaddition,theactivationenergyfordiffusionwas
estimatedtobe65kJmol1(0.5M)and49kJmol1(0.075M).

Chloninebasedionicliquids
In2012Ishiietal.[22]investigatedthephysicalandelectrochemicalpropertiesofcholine
based ionic liquids and their capacity to reduce iron and neodymium cations. The novel
cationic blended ionic liquids which were constituted by the 2
hydroxyethyltrimethylammonium bis(trifluoromethylsulfonyl)imide ChTFSI and P[225]TFSI
wasappliedfortheelectrorecoveryofneodymium.Inthisstudythestartingmaterialswere
voicecoilmotorsforharddiskdriversandtheelectrodepositsobtainedwereexaminedby
SEM/EDXandXPS.Accordingtotheresultsofthisstudy,irongroupandrareearthmetalscan
berecoveredseparatelybyelectrodepositionintwostages.
Preliminarystudiesonlanthanumelectrorecoveryfrompyrrolidiniumbasedionicliquids.
Experimentalworkofthespecificresearchfocusedonevaluatingtheuseofpyrrolidinium
basedionicliquidsfortheelectrorecoveryofreactivemetals,suchastheRareEarthMetals
are. More precisely, the reduction of lanthanum in the ionic liquid NbutylN
methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPTFSI) was studied, at room
temperature.BMPTFSIwasselectedamongthedifferentpyrrolidiniumbasedionicliquids,
because it presents electrochemical stability under cathodic polarisation, satisfying ionic
conductivityanditisanairandwaterstableelectrolyticmedium.
Materialsandapparatus
TheionicliquidBMPTFSIwassuppliedbySolvionicandLanthanumnitratehexahydratewas
purchasedbyAlfaAesar.Thelanthanumnitratesaltwasheatedat100oCundervacuumfor
72handwasdissolvedinpureacetone,wheresubsequentlytheproperamountofelectrolyte
wasaddedtoformasolutionsconcentrationoftheorderof0.06M.Thesolutionwasplaced
at60 oCundervacuumforapproximately2htoremoveacetoneandthenat100 oCunder
vacuumfor24htoremoveresidualwater.
Linear and cyclic voltammetry tests were performed in a three microelectrodes cell (PAR)
connected to a VersaSTAT3 potentiostat (PAR); the obtained experimental data were
analysedwiththeVersaStudiosoftware(PAR).Theworkingelectrodewasaplatinumdiskof
d=1.98mm,asacounterelectrodeaPtwireimmerseddirectlyintothesolutionwasused
andfinally,asareferenceelectrodetheredoxcoupleAg/0,1MAgNO3inacetonitrilewas
employed.Theworkingelectrodewaspolishedwithaluminumpaste1monavelvetpad
and electrochemically in 1 M sulfuric acid. Although BMPTFSI exhibits hydrophobic
characteristicsanditisstableundernormalatmosphericconditions,thecyclicvoltammetry
andchronoamperometrymeasurementswereperformedinaglovebox,providinganinert
atmospherebypurgingnitrogengastominimiseoxygenandmoisturecontamination.The
morphology of electrodeposits was examined by Scanning Electron Microscope
(JEOL6380LV),providedwithEnergyDispersiveSpectrometry.

PAGE|159

ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

Results
The electrochemical window was determined at room temperature by cyclic voltammetry
andthecathodiclimitoftheelectrolytewasdeterminedat3.5VvsAg/Ag+.Figure1shows
thecyclicvoltammogramrecordedinthesystemBMPTFSI/La.Asitisobvious,ageneration
ofanintensecathodicpeakbeginsat2.2VvsAg/Ag+,attributedtothereductionoftrivalent
lanthanumcation(La3+)tothemetallicstate.Theabsenceofcorrespondinganodicpeakon
the reverse scan allows the assumption that lanthanum reduction is irreversible [15].
Moreover,thecathodicpeakat1Visascribedtothelimitedreductionofhydrogencations,
duetoslightmoisture[2]thatinevitablywaspresentandthenarrowshoulderat1,5Vis
attributedtoanadsorptionLa3+reactionoccurringontheelectrode,priortothereductionof
lanthanum[14,15].

Figure1:Cyclicvoltammogramsrecordedwithscanrate20mV/svsAg/Ag+onaPtelectrode
at25oC:(1)BMPTFSIand(2)forthesolutionof0.06MLa(NO3)3inBMPTFSI.

Furthermore,theelectrodepositionoflanthanumwasrealisedonacoppersubstrate,under
potentiostatic conditions for 5 h at 3.1 V (vs Ag/Ag+) at 25 oC. The electrodeposits were
examinedinSEMandEDSanalysis(Figure2)revealedtheelectrodepositionoflanthanum.
TheEDSanalysisalsorevealedtheexistenceoffluorineandsulfurthatmayoccur,duetothe
TFSIanionadsorptionontheelectrode'ssurfacethatcouldexplaintheabsenceofanodic
peak.

PAGE|160

ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

Figure2:SEMimagedepictingtheelectrodepositsoflanthanum(left),
EDSanalysisoftheelectrodeposits(right)
Conclusions
Ionic liquids are promising electrolytes, suitable for the electrodeposition of rare earth
metals. The research in this area has proven their ability to reduce and to permit the
electrodeposition of drastic metals, without the drawbacks present in the currently used
technology.
The preliminary electrochemical investigation of BMPTFSI revealed its potential use for
reduction of lanthanum and appears, due to its physicochemical properties, to be an
appropriatemediumfortheelectrodepositionofrareearthelements.

Acknowledgments
TheresearchleadingtotheseresultshasreceivedfundingfromtheEuropeanCommunitys
SeventhFrameworkProgramme([FP7/20072013])undergrantagreementn309373.This
publication reflects only the authors view, exempting the Community from any liability.
Projectwebsite:www.eurare.eu
References
1.
2.
3.
4.
5.
6.
7.

8.

H.OhnoElectrochemicalaspectsofionicliquids,JohnWiley&Sons,Inc.,Hoboken,NewJersey,(2005).
H.Ohno,in:F.Endres,A.P.Abbott,D.R.Mcfarlane(Eds.),Electrodepositionfromionicliquids,WileyVCH
VerlagGmbH&Co.,2008.
T.Tsuda,C.L.HusseyElectrochemicalapplicationsofroomtemperatureionicliquids,TheElectrochemical
SocietyInterface,Spring2007,4249.
R.E.White,T.Tsuda,C.L.HusseyModernaspectsofElectrochemistryNo45,2009,63174.
Y.Cui,Y.Hua,Y.Lin.Applicationsofionicliquidsinelectrodepositionofrareearths,J.ChongqingUniv:
EngEd[ISSN16718224],2010,9(4):167176.
A.IspasandA.BundElectrodepositionfromionicliquids,TheElectrochemicalSocietyInterface,Spring
2014,4751.
A.Ispas, B. Adolphi, A.Bund, F.Endres. On the electrodeposition of tantalum from three different ionic
liquids with the bis(trifluoromethyl sulfonyl) amide anion J.Phys. Chem. Chem. Phys., 2010, DOI:
10.1039/b922071m.
T.Jiang,M.J.ChollierBrym,G.Dub,A.Lasia,G.M.Brisard.Electrodepositionofaluminiumfromionic
liquids:PartIelectrodepositionandsurfacemorphologyofaluminiumfromaluminiumchloride(AlCl3)1

PAGE|161

ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014
ethyl3methylimidazoliumchloride([EMIm]Cl)ionicliquids,J.Surface&CoatingsTechnology201(2006)
19.
T.Tsuda,T.Nohira,Y.Ito.ElectrodepositionoflanthanuminlanthanumchloridesaturatedAlCl31ethyl
3methylimidazolium chloride molten salts J.Electrochimica Acta ISSN 00134686,2001,46 (12),1891
1897.
T. Tsuda, T. Nohira, Y. Ito. Nucleation and surface morphology of aluminumlanthanum alloy
electrodepositedinaLaCl3saturatedAlCl3EtMeImClroomtemperaturemoltensaltJ.ElectrochimicaActa
ISSN00134686,2002,47(17),28172822.
F.M. Lin, C.L. Hussey. An Electrochemical and spectroscopic study of cerium in the basic aluminum
chloride1methylethylimidazoliumchloridemoltensaltJ.oftheElectrochemicalSociety,1993,140(11),
30933096.
R.C.Jagadeeswara,K.A.Venkatesan,K.Nagarajanetal.Electrochemicalandthermodynamicproperties
ofeuropium(III),samarium(III)andcerium(III)in1butyl3methylimidazoliumchlorideionicliquidJ.of
NuclearMaterial,2010,399(1),8186.
M.Yamagata,Y.Katayama,T.Miura.Electrochemicalbehaviorofsamarium,europiumandytterbiumin
hydrophobicroomtemperaturemoltensaltsystemsJ.oftheElectrochemicalSociety,2006,153(1),E5
E9.
L.M.Glukhov,A.A.Greish,L.M.Kustov.ElectrodepositionofrareearthmetalsY,Gd,YbinionicliquidsJ.
RussianJournalofPhysicalChemistryA,2010,84(1),104108.
S.Legeai,S.Diliberto,N.Steinetal.RoomtemperatureionicliquidforlanthanumelectrodepositionJ.of
ElectrochemistryCommunications,2008,10(11),16611664.
C.J. Rao, K.A. Venkatesan, K. Nagarajan, et al.Electrochemical behavior of europium(III) in NbutylN
methylpyrrolidiniumbis(trifluoromethylsulfonyl)imideJ.ElectrochimicaActa,2009,54(20),47184725.
C.L.HusseyandL.H.Chou.AnElectrochemicalandspectroscopicstudyofNd(III)andPr(III)coordinationin
the1butyl1methylpyrrolidiniumbis(trifluoromethylsulfonyl)imideionicliquidcontainingchlorideionJ.
Inorg.Chem.2014,53,57505758.
Al.Bhatt,I.May,V.A.Volkovich,etal.Structuralcharacterisationofalanthanumbistriflimidecomplex
La(N(SO2CF3)3(H2O)3andaninvestigationofLa,SmandEuelectrochemistryinaroomtemperatureionic
liquid,[Me3NnBu][N(SO2(CF3)2J.Inorg.Chem.2005,44,49344940.
M.Matsumiya,S.Suda,K.Tsunashimaetal.Electrochemicalbehaviorsofmultivalentcomplexesinroom
temperature ionic liquids based on quaternary phosphonium cations J. of Electroanalytical Chemistry,
2008,622(2),129135.
H. Kondo, M. Matsumiya, K. Tsunashima, S. Kodama. Attempts to electrodeposition of Nd from ionic
liquidsatelevatedtemperaturesJ.ElectrochimicaActa66,2012,313319.
A.Kurachi,M.Matsumiya,K.Tsunashima,S.Kodama.Electrochemicalbehaviorandelectrodepositionof
dysprosiuminionicliquidsbasedonphosphoniumcationsJ.Appl.Electroch.,2012,42,961968.
M. Ishii, M. Matsumiya, S. Kawakami. Development of recycling process for rare earth magnets by
electrodepositionusingionicliquidsmediaJ.ECS.Transactions,50(11),549560,2012.

9.

10.

11.

12.

13.

14.
15.
16.
17.

18.

19.

20.
21.
22.

PAGE|162