Welcome to Scribd, the world's digital library. Read, publish, and share books and documents. See more
Download
Standard view
Full view
of .
Save to My Library
Look up keyword
Like this
0Activity
0 of .
Results for:
No results containing your search query
P. 1
ElecActa04

ElecActa04

Ratings: (0)|Views: 10 |Likes:
Published by prathapkumar_1990

More info:

Published by: prathapkumar_1990 on Oct 21, 2010
Copyright:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less

10/21/2010

pdf

text

original

 
Nanostructured CuO thin film electrodes prepared by spray pyrolysis:a simple method for enhancing the electrochemical performanceof CuO in lithium cells
Julia´n Morales
a
, Luis Sa´nchez
a,
*, Francisco Mar´n
b
,Jose R. Ramos-Barrado
b
, Miguel Sa´nchez
b
a
 Departamento de Quı´ mica Inorga´ nica e Ingenierı´ a Quı´ mica, Facultad de Ciencias, Campus de Rabanales,Edificio Marie Curie, Universidad de Co´ rdoba, 14071 Co´ rdoba, Spain
b
 Laboratorio de Materiales y Superficie (Unidad Asociada al CSIC), Universidad de Ma´ laga, Spain
Received 22 December 2003; received in revised form 7 May 2004; accepted 8 May 2004Available online 19 June 2004
Abstract
Nanostructured CuO thin films were prepared by using a spray pyrolysis method, copper acetate as precursor and stainless steel assubstrate. The textural and structural properties of the films were characterized by scanning electron microscopy (SEM), atomic forcemicroscopy(AFM),X-raydiffraction(XRD)andX-rayphotoelectronspectroscopy(XPS).TheSEMimagesrevealedthoroughcoatingofthesubstrate and thickness of 450–1250 nm; the average particle size as determined from the AFM images ranged from 30 to 160 nm. The XRDpatterns revealed the formation of CuO alone and the XPS spectra confirmed the presence of Cu
2+
as the main oxidation state on the surface.The films were tested as electrodes in lithium cells and their electrochemical properties evaluated from galvanostatic and step potentialelectrochemical spectroscopy (SPES) measurements. The discharge STEP curves exhibited various peaks consistent with the processes CuO
,
Cu
2
O
,
Cu and with decomposition of the electrolyte, a reversible process in the light of the AFM images. The best electrode exhibitedcapacity values of 625 Ah kg
À
1
over more than 100 cycles. This value, which involves a CuO
,
Cu reversible global reaction, is ca. 50%higher than that reported forbulkCuO. The nanosize of the particles and thegood adherence of the active material to the substrate are thoughtto be the key factors accounting for the enhanced electrochemical activity found.
ß
2004 Elsevier Ltd. All rights reserved.
Keywords:
Copper oxide; Thin films; Rechargeable lithium batteries; Negative electrode
1. Introduction
In recent years, extraordinary efforts have been made atfinding alternative anodic materials to replace carbon-basedmaterials in Li-ion batteries. One special contribution in thiscontext was the development of the Stalion
1
lithium-ioncell[1]by Fuji Photo Film Celltec. Co. (Japan). Notwith-standing its limited commercial success, the results[2]werewidely celebrated by the scientific community as theyopened up new avenues in the search of alternative materi-als. These studies revealed a high specific capacity in tin-based systems used as anode materials due to their ability toform Li
 x
Sn reversible alloys (1.0
<
x
<
4.4). These findingshave revived interest in traditional and new materials react-ing reversibly with lithium at low potentials, and drewspecial attention to those based on tin[3,4], silicon[5] and intermetallic alloys[6–8]. Two major drawbacksremains to be overcome with a view to facilitating theiruse in the manufacture of lithium batteries, namely: (i) asignificant irreversible capacity loss during the first dis-charge–charge cycle (particularly in oxide-based systems);and (ii) the poor capacity retention resulting from Li-alloy-ing agglomeration.
www.elsevier.com/locate/electactaElectrochimica Acta 49 (2004) 4589–4597* Corresponding author. Tel.: +34 957 218620; fax: +34 957 218621.
E-mail address:
luis-sanchez@uco.es (L. Sa´nchez).0013-4686/$ – see front matter
ß
2004 Elsevier Ltd. All rights reserved.doi:10.1016/j.electacta.2004.05.012
 
An alternative approach to the development of anodicmaterials have been recently reported by Poizot et al.[9].They found 3d-transition metal oxides (M
 x
O
 y
, M = Co, Ni,Cu, Fe) to reversibly react with Li ions at low potentials. Asimple, yet brilliant, lithium reaction mechanism was putforward to account for the reversibility observed[9
11]andsummarized by the simple reaction:M
 x
O
 y
þ
2
 y
Li
,
 x
M
þ
 y
Li
2
O
:
(1)The Li
2
O formed in the reduction process behaves as anelectrochemically active material in the reverse reaction.The origin of this behaviour, previously unknown, wasascribed to the nanometric nature of the metal particlesformed. It is thus believed that, in this aggregation state,the particles possess and enhanced electrochemical reactiv-itytowards theformation/decompositionofLi
2
O[9].Infact,nanostructured materials have emerged as attractive alter-natives to conventional materials by virtue of their promi-nent electronic and chemical properties[12]. Thesetransition metal oxides can retain capacity values as highas 700 Ah kg
À
1
on extended cycling. These valuesclearly exceed those of graphite-based anodic materials(theoretical gravimetric capacity 372 Ah kg
À
1
) and havebeen deemed future candidates to replacing these carbonac-eous materials. Thus, various transition metal oxides(Co
3
O
4
15], Fe
2
O
3
[16], LiFeO
2
[17], Li
5
FeO
4
[17]) were recently examined as anodic materials for Li-ion batteries. This idea was
rst suggested for Fe
2
O
3
byMorzilli et al.[18], who did not address the reactionmechanism involved, however.Among these transition metal oxides, CuO possessesattractive advantages. Thus, it is an inexpensive, non-toxiccompound used in the manufacture of Li/CuO primary cells[19,20].Recently, the electrochemical reactivity of CuOtowards lithium was revisited by De
´
bart et al.[21]demon-strated the reversibility of reaction (1) for CuO, whichinvolves the formation of Li
2
O, Cu and Cu
2
O nanograinsasintermediates.However,Grugeonetal.[10]foundthattheCuOcelltodeliverasustainedreversiblecapacityofonlyca.400 Ah kg
À
1
(i.e. similar to that observed for Cu
2
O) uponextended cycling. This means that more than a 50% of theCuO theoretical capacity, referred to its reduction to Cu, isunavailable.The spray pyrolysis method is a well-known nanostruc-tured thin-
lm preparation method with excellent featuressuch as the need for no sophisticated equipment, and qualitytargets or substrates; also,
lm thickness and stoichiometryare easy to control and the resulting
lms are well com-pacted. We have used this coating method to prepare thin
lms of nanosize active material for lead
acid and lithiumbatteries[22,23]. In this work, we extended this method tothe preparation of nanocrystalline CuO thin
lms andexplored their activity as electrodes in lithium batteries.This synthetic procedure results improves the electroche-mical reactivity of CuO compared with the bulk material.The reversibility of the CuO
,
Cu reaction is enhanced andthe cell can deliver high, sustained speci
c capacity valuesupon extended cycling.
2. Experimental
A previously reported spray pyrolysis method[24],was used to prepare the CuO coatings. An aqueous solutionof 0.05 M Cu(CH
3
COO)
2
was used as precursor. Thesolution was pumped into the air stream in the spraynozzle at a rate of 50 mL h
À
1
by means of a syringe pump,for a preset time of 30 and 80 min. An air stream of 25 L min
À
1
, measured at 1.25 bar, was used to atomizethe solution. Circular disks of commercial 304 stainlesssteel (0.4 mm thick and 7.5 mm in diameter) were used assubstrate. They were kept at temperatures over the range of 200
300
8
C. The amount of oxide attached to the substratewas determined by weighting the electrode before and afterdeposition using a Sartorius microbalance with a sensitiv-ity of 
Æ
1
m
g. X-ray diffraction (XRD) patterns wererecorded on a Siemens D5000 X-ray diffractometer, usingCu
a
radiation and graphite monochromator, in steps of 0.02
8
and 1.2 s. Scanning electron microscopy (SEM)images were obtained on a Jeol JMS-5300 microscope.Topographic AFM examinations were performed by usinga Nanoscope IIIa contact-mode AFM (Digital Instru-ments). Type NP cantilevers (Digital Instruments) withSi
3
N
4
tips and a spring constant of 0.58 N m
À
1
wereemployed. In order to avoid exposure to the air, a seriesof precautions were adopted in recording the AFM imagesof the discharged and charged electrodes. Thus, the elec-trodes were covered with a layer of propylene carbonateinside of a dry-box and rapidly transferred to the liquid cellof the AFM microscope. In this manner, the electrodesurface is protected against the exposure to water oroxygen during the measurement and the results mustre
ect the changes undergone by the electrode surfaceinside the electrochemical cell.X-ray photoelectron and X-ray excited Auger spectrawere obtained with aPhysical ElectronicsPHI 5700 spectro-meter using non-monochromated Mg K 
a
radiation (
h
n
=1253.6 eV) and a hemispherical analyser operating at con-stant pass energy of 29.35 eV. Spectra were recorded withthe X-ray generator operated at 15 kV and 20 mA. Theenergy scale of the spectrometer was calibrated using theCu 2p
3/2
, Ag 3d
5/2
and Au 4f 
7/2
photoelectron lines at 932.7,368.3 and 84.0 eV, respectively. The vacuum in the analysischamber was better than 10
À
9
mbar. Binding energies werecorrected using the binding energy values for C 1s of adventitious carbon (and for the methyl group)
xed at284.8 eV. Samples were mounted on a holder without adhe-sive tape and kept under high vacuum in the preparationchamber overnight before they were transferred to theanalysis chamber of the spectrometer. Survey spectra overthe range 0
1200 eV were recorded at a 187.85 pass energy,each region being scanned several times to ensure an
 J. Morales et al./Electrochimica Acta 49 (2004) 4589
 – 
4597 
4590
 
adequate signal-to-noise ratio. A 3 mm
Â
3 mm sample areawas sputtered with 4 keVAr
+
; the sputter rate was assumedto be
$
0.3 nm min
À
1
as determined for Ta
2
O
5
under iden-tical sputtering conditions. Spectra were processed usingPHI-Access V.6 and Multipak software, both from PhysicalElectronics. Curve
tting of high-resolution spectra wasdone after Shirley background correction and satellite sub-traction. Surface atomic concentrations were determinedfrom peak areas, using Shirley background subtractionand sensitivity factors provided by the spectrometer man-ufacturer (Physical Electronics, Eden Prairie, MN). In orderto avoid the reduction of copper oxide by the X-ray as far aspossible,thedatafortheCu2pregionwerecollectedatshortacquisition times. For ex situ XPS measurements once thecell was dismantled, the pellet was washed with hexane. Allthese manipulations were performed in argon atmosphereand a special glove-box connected to the antechamber of thespectrometer allowed to transfer the sample into the spectro-meter avoiding a direct contact with air.Electrochemical measurements were carried out in twoelectrodes cells, using lithium as counter-electrode. Theelectrolyte used was Merck battery electrolyte LP 40(EC:DEC=1:1(w/w)1 MLiPF
6
).Circulardisksofstainlesssteel coated with the active material were used as workingelectrodes. The cells were galvanostatically charged anddischarged at a current density of 0.075 mA mg
À
1
(
 /5cycling rate,
being de
ned as one Li
+
exchanged in1 h). The SPES curves were recorded with regime of 75 mV h
À
1
per step. All electrochemical measurementswere controlled via a MacPile II potentiostat
galvanostat.
3. Results and discussion
Different coatings were prepared by changing the heatingtemperature of substrate and the time of deposition of thecopper(II) acetate solution.Fig. 1shows the XRD patternsfor the samples prepared under the experimental conditionsshown inTable 1. The low signal to noise ratio reveals a lowcrystallinity in the samples. The XRD patterns exhibit twomain signals at 35.6
8
and 38.7
8
2
that can be ascribed to the(
À
1 1 1) and (1 1 1) re
ections of the CuO phase[25]. Peak intensities and hence crystallinity increased with increasingtemperature and, especially, increasing deposition time.Although the low crystallinity of the particles, re
ected insubstantial broadening of peaks, precluded the accurateidenti
cation of the Cu
2
O phase in the
lms, the absenceof the (1 1 1) re
ection, located at a rather different spacingfrom those of CuO, allows one to discard its formation underthe deposition conditions used.SEM images revealed thorough coating of the substrate.The
lms are highly dense and uniform, which makes itdif 
cult to distinguish individual particles. Thevalues of the
lm thickness, estimated from cross-sectional SEM images(Fig. 2a), are shown inTable 1. Complementary information of the
lm morphology was obtained from AFM images,which alsoexposedthe highuniformity of the
lms obtainedwith all the treatments and revealed that they resulted fromthe agglomeration of round-shape nanoparticles (seeFig.2b). Particle size was calculated by averaging the resultsof several AFM observations in different regions of the
lms (Table 1). The evaluation of the crystallite sizefrom the main re
ections of the XRD patterns was hinderedby the low resolution of the peaks. Only for sample F,where crystallinity is clearly enhanced, one can obtainreasonably accurate values. Crystallite size obtained from
 J. Morales et al./Electrochimica Acta 49 (2004) 4589
 – 
4597 
4591
3035404550
2 degrees
θ
Sample FT =300 ºCSample ET =250 ºCSample DT =200 ºC
**
1111111103035404550
Sample CT =300 ºCSample BT =250 ºCSample AT = 200 ºC
**
CuOCu
2
O111111
2 degrees
θ
Fig. 1. XRD patterns for CuO thin
lms. The asterisk denotes diffractionlines corresponding to the substrate.Table 1Experimental preparation conditions and physical characteristics of the CuO thin
lmsSample Temperature (
8
C) Time (min) Mass deposited (mg cm
À
2
) Thickness
a
(nm) Particle size
b
(nm)A 200 30 0.36 660 20
60B 250 30 0.30 475 40
75C 300 30 0.17 420 25
60D 200 60 0.58 1100 80
200E 250 60 0.56 1150 60
180F 300 80 0.73 1250 100
220
a
Estimated from SEM images.
b
Estimated from AFM images.

You're Reading a Free Preview

Download
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->