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Electrochimica Acta
jou rn al hom epa ge: www.elsev ier .com/ locate /e lec tac ta
hin copper phosphide films as conversion anode for lithium-ion batterypplications
.S. Chandrasekar, Sagar Mitra ∗
lectrochemical Energy Laboratory, Department of Energy Science and Engineering, Indian Institute of Technology Bombay, Mumbai 400076, India
r t i c l e i n f o
rticle history:eceived 13 September 2012eceived in revised form1 November 2012ccepted 26 December 2012vailable online 8 January 2013
a b s t r a c t
Air stable copper phosphide of thicknesses (0.2, 0.4 �m) was synthesized over copper plates (of 10 mmdiameter) by hybrid electrochemical deposition and low temperature solid-state reaction. Stoichiometricamount of red phosphorus (P) were sprayed over electrodeposited copper and followed by annealing at250 ◦C under inert gas atmosphere for different durations (5 h, 7 h and 12 h). During this process, phospho-rus particles diffuse by excavating into the copper deposits, producing holes, where the Cu3P crystallitesnucleate and lead to conglomeration of several agglomerates and hence resulted in non-homogeneous
eywords:opper phosphideonversion reactionlectrochemical and solid state methodsnergy storage anode material
morphology. A small extend of Cu3P oxidation occurs over the film’s top surface. X-ray diffraction (XRD)patterns confirm that the layer to be pure Cu3P. Scanning electron microscopy (FEG-SEM) reveals a porousmicrostructure consisting of agglomerated particles with ∼10 �m size. The as-prepared carbon-free Cu3Pelectrodes exhibited significantly improved capacity retention and rate capability characteristics over 40cycles when electrochemically tested against lithium at constant 20 �A/cm2 rendering it as possible
h ene
ithium-ion Battery negative electrode for hig
. Introduction
Electric energy is required for several day to day applicationsnd hence considered as bloodline for sustaining this modern soci-ty. Though, electricity could be generated by both renewable andon-renewable sources, the challenge lies on its storage [1]. Apart
rom myriad applications, stored form of this energy is essential forortable electronic devices and visualizes long run electric vehiclesEVs) [2–5] due to fast consumption of fossil fuels. For this applica-ion, electrochemical devices like battery and supercapacitor wereest considered. Since the introduction of rechargeable lithiumatteries in early 80’s, lithium-ion batteries (LiBs) have under-one several developments in all aspects, and are now regardeds “Heart” for modern electronics due to its high power/energyensity [1,4].
Today’s immerse research on LiBs are devoted towards mate-ial chemistry [6] in discovering the best combination of anode andathode as a replacement for commercialized graphite and LiCoO2,hich is based on intercalation–deintercalation mechanism [7,8].
heir performances are limited due to structural inability involvingnly 0.5Li+ transfer during cycling. High energy LiBs are foreseen
sing Sn, Si, Zn etc. as negative electrodes whose capacities are 3o 10 times higher than graphite. Huge volume change occurs dur-ng cycling, limits these materials from being commercialized [8].
The discovery of conversion reaction involving reversible reactionof 2 or more e− of metal oxides with lithium [9], prompt the explo-ration for other Metal–X compounds with X = O, N, F, S, P and evenH [9–23] as possible negative electrodes for high energy densitylithium-ion battery (LiB) applications. A typical conversion reactionequation could be given as: MaXb + (b·n) Li → a M + b LinX. The pos-sible explanation for reversibility of conversion reaction dependson the formation of metal nanoparticles over lithium binary com-pound (LinX) matrix upon complete reduction and the former beingvery active due to possession of large amount of interfacial surfacehelps in decomposition of LinX matrix when reverting the polarityof the circuit. This nanometric character of the metal nanoparticleshas shown to be maintained over several redox cycles [8,9,21].
The major limitations of conversion reactions are poor kinet-ics, marked by large hysteresis in voltage between charge anddischarge and poor capacity retention upon cycling [8,11]. There-fore, for its effective utilization in practical cells, it is imperativeto reduce this hysteresis which limits LiB’s energy efficiency andpower capabilities. From several literatures, it is noted that thepolarization (�V) decreases from fluorides (�V ∼ 1.1 V) to oxides(�V ∼ 0.9 V), sulfides (�V ∼ 0.7 V) and phosphides (�V ∼ 0.4 V)[7,8,21]. This is due to the fact that the redox centres are not exclu-sively located on the transition metal, but electron transfer alsooccurs into the bands that have a strong anion contribution. It
was shown that the actual potential at which conversion occursdepend on both the transition metal and the anionic species, so that,in principle, its reaction potential could be tuned to the requiredapplication [8].
Apparently, metal phosphides may be an option as anodic mate-ials [19–22] for LiB applications for above reasons. Phosphorusorms solid compounds with nearly all the elements in the periodicable, but its presence are less known unlike others [24]. However,he syntheses of all these materials is usually complicated as theseequires the use of special devices, such as vacuum sealed tubes andave to be handled and stored under inert atmospheres and hencerevent it from realization for industrial preparation. Metal phos-hides (MxPy) could be synthesized viz., high temperature solidtate technique [25,26], ball milling [27,28] and low temperatureydro- and solvo-thermal methods [29–31].
Copper forms three phosphorus compounds (Cu3P, CuP2 andu2P7) according to Cu–P phase diagram [24]. Among them, onlyu3P is air stable and already presents industrial applicationss a kind of fine solder and as an important alloying addition31]. Copper phosphide (Cu3P) presents good qualities as neg-tive electrode. Since no Li–Cu compounds have been reportedn the corresponding phase diagram, the reaction in which the
aximum lithium uptake of the elements is admitted could be:Cu3P + 3Li → 3Cu + Li3P). Though, gravimetric capacity of Cu3P377 mA h/g) is close to that of graphite (372 mA h/g), but its volu-
etric capacity (2778 Ah/L) is almost four times higher than thatf graphite (800 Ah/L) [19,26,29,32].
As mentioned earlier, like other metal phosphides, Cu3P pow-ers/films were synthesized by similar techniques [25–31] andubsequently, its electrochemical cycling were tested. The mainrawbacks of these methods were requirement of (1) absolute inerttmosphere due usage of air sensitive chemicals and (2) high tem-erature (400–900 ◦C) for solid state synthesis. After these carefulonsiderations, herein, we presented a hybrid technique to producearbon-free Cu3P thin films over Cu current collector and firstly,eported the effect of various film thicknesses and annealing timen its electrochemical reactivity against lithium.
. Experimental
A typical hybrid electrochemical deposition and low tempera-ure solid state synthesis were employed to envision the product,u3P. This section would elaborate on material synthesis andetails of instrumentation for materials characterization.
.1. Synthesis of Cu3P material over Cu plate
.1.1. Electrochemical deposition of copperPulse electrodeposition (using AUTOLAB, PGSTAT 302N,
etrohm) was carried out in a 50 mL capacity cell from an alka-ine electrolyte [10,11] consisting of 100 g/L CuSO4·5H2O (Sigmaldrich), 20 g/L (NH4)2SO4 (Sigma Aldrich) and 80 mL/L diethyl-tri-mine (DETA, Sigma Aldrich) to electrodeposit copper of varioushickness (2.5, 1.5, 0.8, 0.4, 0.2 �m). Prior to electrodeposition,he Cu plates (of 10 mm diameter) were polished following theseuccessive steps, with 800, 1200 and 2400 grit sand paper and thenith 6, 3, 1 and 0.25 micron diamond suspension using a polishing
loth. After this last step, copper disc surfaces exhibited a mirrorook meaning that an object is perfectly reflected without anyeformation. Copper deposits were obtained by electrodepositingor appropriate duration (using Faraday’s I law of electrolysis)hile assuming 99% electrolyte’s current efficiency. All elec-
rodeposition experiments were carried out at room temperature30–32 ◦C).
.1.2. Low temperature solid state synthesis
Firstly, calculated stoichiometric amount of red phosphorus
Spectrochem Pvt. Ltd., Mumbai) for each deposit were dispersedn acetone using ultra-sonicator and were uniformly sprayed over,espective, electrodeposited copper plates. Each set of samples
chimica Acta 92 (2013) 47– 54
were heated at 1 ◦C/min in tubular furnace (Thermo Scientific, Lind-berg Blue M) under an inert (N2 gas) atmosphere at constant 250 ◦Cfor different durations like 5 h, 7 h and 12 h. The samples werecollected after cooling to room temperature (32 ◦C) and the samewere characterized for phase composition, morphology and elec-trochemical studies against lithium.
2.2. Phase composition and morphology characterization ofcopper phosphide films
X-ray diffraction (XRD) measurements were performed withX’PERT PRO PANalytical (Model: PW3040 160 X’Pert PRO,Netherlands) equipped with Cu K� radiation. XRD patterns werecompared with JCPDS data to identify the phase of each samples.
Field Emission Gun – Scanning Electron Microscope (FEGSEM)(JOEL, Model: JSM-7600F, Japan) coupled with energy dispersiveX-ray (EDX) was used to characterize the surface morphology andcompositional analysis of copper phosphide films. The instrumentwas operated at 0.1–30 kV.
2.3. Electrochemical behaviour with lithium
Swagelok-type cells were assembled in an argon-filled dry glovebox (Mbraun, MB10 compact) using the Cu3P thin films as the pos-itive electrode and the Li metal as the negative electrode. Bothpositive and negative electrodes were electronically separated bya Whatman GF/D borosilicate glass-fibre sheet saturated with 1 MLiPF6 electrolyte solution (in EC:DMC/1:1 in mass ratio) purchasedfrom Merck. Unless it is specifically stated, otherwise, the cells weregalvanostatically cycled (in Arbin Instrument’s BT2000) between0.01 V and 2.5 V at constant 20 �A/cm2. In-situ impedance spec-troscopy at various potentials during first discharge–charge cyclewere measured using Biologic Science Instruments (Model: VMP3;S/n: 0398) between 0.1 MHz to 10 mHz under AC stimuli with 5 mVof amplitude.
3. Results and discussion
Fig. 1 shows the overall morphology of the electrodepositedcopper over Cu plates/discs. These deposits were obtained atconstant current densities of −2 and −30 mA/cm2. The latterhave well-defined grain boundary and adherent/compact deposits[33] as compared to former conditions. The deposits obtained at−2 mA/cm2 were utilized for rest of the experiments since it wouldpermit the fast reactivity and P diffusion while heating to form Cu3Pthin films.
Preliminary experiments were made at various temperaturesbetween 250 ◦C to 400 ◦C for constant 5 h duration. To the surprise,pure Cu3P phase was obtained at minimum temperature of 250 ◦Cwhile distinct Cu oxidation to cuprous oxide and sublimation ofP occurs at elevated temperatures. Hence, the temperature wasfixed at 250 ◦C and thereon, studied the effect of heating time whichwould play a vital role in the conversion of Cu deposits of differentthicknesses to copper phosphide which in turn would determinethe kinetics between the active materials (Cu3P) and Cu currentcollector [10,11].
3.1. Phase and compositional analysis
Fig. 2 shows the different XRD patterns obtained for the Cu–Pdiscs, heat treated at 250 ◦C for various time 5 h, 7 h and 12 h,respectively. With the exception of the reflections owing to metallic
copper of the substrate, the XRD pattern of the heat treated copperdeposits reveal Bragg peaks which can all be indexed on the basis ofa hexagonal cell with the following lattice parameters: a = 6.992 Aand c = 7.170 A, and P3cl space group (JCPDS No.: 74-1067). XRD
M.S. Chandrasekar, S. Mitra / Electrochimica Acta 92 (2013) 47– 54 49
lates/d
pot
tpl(eotaC
dtf
F5
Fig. 1. Electrodeposited copper over Cu p
atterns of these samples presented the typical diffraction patternf Cu3P. In addition, the intense and sharp diffraction peaks suggesthe obtained product was well crystallized.
Herein, we tried to study the effect of heating time at constantemperature (250 ◦C) on texture and morphology of the sam-les, which in turn, affect its electrochemical performance against
ithium. For 5 h heating time, the preferred orientations like (3 0 0),1 1 3), (1 1 2), (2 1 1) and (2 1 0) planes of the as-obtained samplesxactly match the standard JCPDS pattern as compared to othersbtained at longer durations (say 7 h and 12 h). At longer heatingime, the grain align along (1 1 2) directions while growth decreaseslong (3 0 0) and (1 1 3) planes. Other Cu–P phases like CuP2 andu2P7 could not be attained under any circumstances.
Copper was the only transition metal of the first series that pro-uced a phosphide at low temperatures by direct reaction betweenhe metal and phosphorus. The enthalpies of formation at 298.15 ◦Cor different metal phosphides have been reported previously [24].
ig. 2. XRD pattern of as-obtained Cu3P samples of various thickness (1–0.2 �m, 2–0.4 �m h; (b) 7 h and (c) 12 h.
isc: (a) −2 mA/cm2 and (b) −30 mA/cm2.
The enthalpy values for the different transition metal phosphidesdo not show any kind of trend. According to Pfeiffer et al. [19] thepossible explanation could be that all the elements of the first tran-sition series have partially filled 3d shells, except copper and zinc.Nevertheless, only the copper has a complete 3d shell, and a sin-gle 4s electron outside the 3d shell [19]. Then, copper is the onlyelement in the series to have M+1 state. This unique electronic con-figuration may facilitate the solid-state reaction between copperand phosphorus (3Cu + P → Cu3P). Furthermore specific experi-ments have to be performed to probe completely this hypothesis[19].
3.2. Morphology and surface analysis of the Cu3P films
The surface morphologies of the Cu3P films produced over theCu plates at 250 ◦C are depicted in Figs. 3 and 4. Low magnificationof 5000× was selected to compare the overall grain morphology
, 3–0.8 �m, 4–1.5 �m and 5–2.5 �m) heated at 250 ◦C for various duration like (a)
50 M.S. Chandrasekar, S. Mitra / Electrochimica Acta 92 (2013) 47– 54
Fig. 3. SEM images of Cu3P of various thickness obtained at different heating times: (a–c) 5 h; (d–f) 7 h; (g–i) 12 h; (a, d, and g) 0.2 �m; (b, e, and h) 0.4 �m; (c, f, and i) 0.8 �m.
Fig. 4. SEM cross-section images of 0.4 �m thick samples annealed at (a) 5 h; (b) 12 h and their corresponding EDX analysis.
M.S. Chandrasekar, S. Mitra / Electro
Table 1EDX compositional analysis of 0.4 �m thick samples annealed at (a) 5 h; (b) 12 h.
Elements Sample (a)Composition (at.%)
Sample (b)Composition (at.%)
aiwts
tapacffi(otdEva
3
iCor
Cu 68.97 51.20P 23.62 17.71O 7.41 31.09
nd its distribution (Fig. 3). In general, the Cu3P films presented annhomogeneous and porous structure, produced by agglomerates
ith a particle size ranging from 4 �m to 20 �m. A closer examina-ion of these agglomerates showed that they were made of <1 �mized tiny particles.
Fig. 4 shows the cross sectional view of 0.4 �m thick sampleshat were annealed for (a) 5 h, (b) 12 h and their EDX compositionalnalysis are tabulated (Table 1). Phosphorization of electrode-osited copper to Cu3P occurred to different magnitude; althoughtomic ratio of Cu to P was ∼3:1 (excluding O) was maintained asonfirmed by XRD analysis. Also, low heating time (5 h) leads toormation of non-adherent, porous large particles (Fig. 3a–c) whilene, adherent deposits were obtained with long annealing timeFig. 3g–i). The latter may be due to the diffusivity of phosphorusver Cu grain boundary leading to formation of Cu3P as comparedo former case. Also, the top surfaces of the films were partially oxi-ized and its extent increased with annealing time as analyzed fromDX data (Table 1). The morphology observed, for the Cu3P films, isery convenient and useful to allow the electrolyte impregnationnd a good reactivity during the electrochemical test.
.3. Electrochemical testing of Cu3P films against lithium
According to available literatures [19,26,29,32,34–36], the max-
mum lithium uptake by Cu3P during first discharge is given as:u3P + 3Li → 3Cu + Li3P, therefore, a reversible theoretical capacityf 377 mA h/g or 2778 Ah/L could be envisioned. As the volumet-ic capacity of Cu3P is 70% higher than the commercial graphite
Fig. 5. Electrochemical reactivity of Cu3P (of 0.2 �m, 0.4 �m, 0.8 �m thickness a
chimica Acta 92 (2013) 47– 54 51
(800 Ah/L), could have made it to be the subject of study as neg-ative electrode for LiB applications. Among pertinent papers, fewwere reported as carbon free electrodes and therefore, herein, anattempt was made to study the electrochemical behaviour of thesame without any further treatment. All films were cycled between0.01 V and 2.5 V against lithium under galvanostatic condition withan applied current density of 20 �A/cm2 (unless otherwise stated).
Fig. 5a–c shows capacity vs. voltage (vs. Li+/Li0) plots of 0.2,0.4 and 0.8 �m thicknesses obtained at different annealing timeof 5 h, 7 h and 12 h, respectively. All plots depict the complexityof mechanism involved in the phase transformation of Cu3P uponcycling against lithium. During first cycle, irrespectively of heat-ing time, 0.4 �m thick sample out performed others by providinggood reversible capacity. As a general trend, the best cyclability wasobtained for films of less thickness since it decrease the diffusionlength while preserving an effective electronic percolation [10,11].
The potentiodynamic plot in Fig. 6a and b clearly predicts theseries of complex electrochemical mechanism undergone by Cu3P,particularly during first discharge–charge cycle. The peaks in Fig. 6ashowed that above 1 V, three, respective, irreversible electrochemi-cal processes took place during 1st discharge cycle correspondinglyat: 1.84 V (1), 1.52 V (2), 1.28 V (3). The irreversible peaks above1 V may be due to following reasons: (a) intercalation of Li+ intopristine Cu3P upon discharge [36]; (b) formation of solid elec-trolyte interface (SEI); (c) reaction of amorphous copper oxidewith Li+ [19,26,34]. Upon further discharging to 0.01 V, a plateauregion starting at 0.92 to 0.77 V could involve the conversion ofCu rich (LiCu3P) phase to Li rich (LixCu3−xP) phase of Li–Cu–Psystem and its subsequent reduction to copper metal nanoparti-cles embedded over polymer Li3P compound at lower potential.Moreover, a reduction reaction below 0.25 V could have origi-nated from electrolyte reduction on nanoscaled metal particles
as reported earlier for other metal phosphides [19]. Accordingly,the overall pathway that could be proposed in 1st discharge as:Cu3P + Li → LiCu3P → LixCu3−xP → Cu + Li3P. The second and thirddischarge cycles (Fig. 6b) produced similar trend (peak A to peak
nd annealing time) against lithium: (a) for 5 h; (b) for 7 h and (c) for 12 h.
52 M.S. Chandrasekar, S. Mitra / Electrochimica Acta 92 (2013) 47– 54
F ith gaa e–cha
Dpmm
cacprapcootdvacb
ig. 6. Potentiodynamic plot (a) first cycle and (b) 2nd and 3rd following cycles wnd (c) impedance spectroscopy analysis at respective voltage during first discharg
) and differed remarkably from first only in terms of reductioneak’s intensity, hence showed decreased in performances whichay be due to microstructural and/or structural changes of activeaterial.Upon charging (Fig. 6a), four distinct electrochemical pro-
esses (7)–(10) proceeded correspondingly at: 0.82 V, 1.06 V, 1.13 Vnd 1.27 V which were in well co-ordination with galvanostaticurves at respective potentials. Accordingly, Li rich (LixCu3−xP)hase decreased with increased potential leading to form Cuich LiCu3−xP phase. As per archive, the sharp peak at 1.06 Vnd 1.13 V were due to delithation process to form amorphoushase, LiCu3−xP phase. The irreversible capacity loss during 1stycle may be due to formation of lithiated Cu–P phase insteadf actual Cu3P and also irreversible formation of metal oxiden charging [9,10]. Also, oxidation peaks of the second andhird cycles (Fig. 6b) were well positioned similar to first butiffered only in terms of capacity. However, the first cycle irre-ersibility is high which reduces on consecutive cycles which
re reflected in columbic efficiency (Fig. 7a). This irreversibilityan be explained (i) by the presence of copper oxide(s) and (ii)y the electrolyte reaction increased by the higher surface area
lvanostatic curve at constant 20 �A/cm2 for Cu3P/Li from 0.01 V to 2.5 V vs. Li/Li+;rge cycle.
electrode/electrolyte. Impressive, normalized discharge and chargecapacity (towards the geometrical surface area) of 1.38 mA h/cm2
and 0.61 mA h/cm2, respectively, were obtained for 5 h heatingtime.
Preliminary attempts were made to study the kinetics [37–39]involved during first discharge–charge process of Cu3P when sub-jected to 5 mV of amplitude AC stimuli in 0.1 MHz to 10 mHzfrequency range. Fig. 6c shows the Nyquist plots of the electrodeat different discharge–charge states in the first cycle. The shapeof Nyquist plot of electrode at OCP consists of a depressed semi-circle formed by overlapping of high- (HF) and medium frequency(MF) semicircles with a long inclined low-frequency line (LH). Bydischarging the Cu3P electrode to 0.01 V, produced Nyquist plotswith negligible HF, distinct MF and a inclined line towards real part(i.e., x-axis). The reverse plots were observed on charging the elec-trode to 2.5 V. The as-obtained Nyquist plots were fitted with modelcircuit in order to propose a prototype of the electrode system.Accordingly, the experimental plot exactly fits a model consisting
of: a resistor (Rs) in series with two parallel components, capacitor(Cdl) and another resistor (Rct) followed by Warburg (W) diffusioncomponent [39–41].
M.S. Chandrasekar, S. Mitra / Electro
F
trpewvbSvclscu
TI
ig. 7. (a) Cycle number vs. capacity (mA h/cm2) and (b) its rate capability plot.
In order to reach the active material (Cu3P), during discharge,he diffusion of Li+ ions have to encounter firstly (a) the electrolyteesistance (Rs) followed by (b) double layer (Cdl) and finally (c) aassivity layer (Rct) formed over electrode when latter soaked inlectrolyte. Generally, the depressed semicircle in high frequencyas related to the resistance of the surface-passivating layer. Rs
alues were low and stable until 1.52 V and 1.27 V which coulde due to formation of lithiated Cu–P phase upon discharging.EI formation at lower potential (<0.77 V) was reflected in the Rct
alues (Table 2) [40,41]. The small MFS could be indexed to theharge transfer resistance (Rct) on SEI, and the following inclinedine corresponded to the Warburg impedance of Li+ diffusion in
olid material. Upon charging, the values of Rs and Rct decreasedontinuously due to the initial SEI’s decomposition while Cdl val-es increased which were vice versa during discharge. More insight
able 2mpedance spectroscopy data at each stage during first cycle.
into electrochemical impedance spectroscopy is required for betterunderstanding of kinetics involved in Cu3P cycling.
Fig. 7b depicts the rate capability plot of 0.4 �m thick Cu3P filmcycled at different rate starting from C/20, C/10, C/5, C/2, 1C, 2C,5C, 10C and then revert back to C/20 rate. At each rate, ten cycleswere run to test its retention capacity. Indeed, the Cu3P of 0.4 �mthick exhibited comparatively good capacity retention capabilitythan other films. The performance improvement of this carbon-free phosphide electrode is linked to (i) an ideal chemical interfacebetween Cu3P active material and copper current collectors (theelectronic transport is optimized), (ii) a high interface surface areabetween the active material and the liquid electrolyte (the ionictransport is optimized) and (iii) a buffering of the volume variationsupon cycling by the porous nature of the material. The enhance-ment of the interface contacts aims at countering kinetic limitationsof phosphide active materials.
4. Conclusions
Cu3P films of various thicknesses were prepared by anneal-ing copper discs containing red phosphorus sprayed over copperdeposits at constant 250 ◦C for different durations. All depositscontained pure Cu3P phase with small amount of Cu2O while thelatter quantity increased with annealing time. This was confinedby both XRD and EDX analysis. The morphology of these filmswas characterized with micron-sized grain that may be formedby agglomeration, thereby, making it non-homogeneous both instructure and composition. All films were tested electrochemicallyagainst lithium between 0.01 V to 2.5 V at constant 20 �A/cm2.Cu3P of 0.4 �m thick deposits obtained at various heating timesexhibited enhanced reversibility in first cycle as compared toother films. Hence, this was optimized for further electrochem-ical characterizations which in turn demonstrated excellent ratecapability and capacity retention when cycled at different rateagainst lithium. Its performance could still be improved by fab-ricating nano-architectured electrode containing Cu3P over coppernanorods.
Acknowledgements
The authors are grateful to DST-Nano Mission, New Delhi forfinancial support to carry out this research work. Also, we expressour thanks to SAIF, IITB and Research Scholars for providing ade-quate instruments facilities in meeting the characterizations ofthese materials.
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