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Symposium in Honour of Professor Lauri E.

Holappa
Metal Separation Technologies III of the Helsinki University of Technology

Aluminum Electrolysis in Ionic Liquids at Low Temperature


VENKAT KAMAVARAM and RAMANA G. REDDY

Ionic liquids are new salts used as potential non-aqueous electrolytes for aluminum electrolysis at low
temperatures. The ionic liquid electrolyte used in the present study consisted of AlCl3 and 1-methyl-3-
butylimidazolium chloride (BmimCl). Electrolysis in ionic liquid electrolyte was utilized for (i) aluminum
reduction from electrolyte and (ii) electrorefining of aluminum alloys. Effect of experimental parameters such
as temperature, applied voltage and concentration of electrolyte on electrolysis process was studied. High purity
aluminum (>98%) deposits were obtained on copper cathode. Low energy consumption and no pollutants
emission are the main advantages of this process. The initial stages of aluminum deposition on copper were
studied using cyclic voltammetry and chronoampereometry techniques. The kinetics of electrodeposition was
found to be quasi-reversible with a charge transfer coefficient () of 0.4. Chronoamperograms obtained at
voltages ranging from -0.1 to -1.0 V revealed that the initial stage of aluminum deposition was instantaneous
nucleation followed by diffusion controlled growth of three-dimensional nuclei. The diffusion coefficient of
electroactive species Al2Cl7 was found to be 6.5107 cm2s1 from Cottrell equation and 3.9107 cm2s1 from
the dimensionless current-time transients. The diffusion coefficients for aluminum deposition observed in the
present study compared well with that available in the literature.

I. INTRODUCTION Nucleation and growth phenomena during aluminum


deposition were previously observed in AlCl3-NaCl [15],
AlCl3-LiAlH4-THF [16], AlCl3-DMSO2 [17] and EmimCl-AlCl3
ALUMINUM is generally extracted from its ore by the [18]
melts. The salient feature of aluminum deposition process
well established electrolytic process, Hall-Heroults process. is a nucleation phenomenon followed by diffusion controlled
Since aluminum has very high negative reduction potential, growth of three-dimensional centers was observed in all the
electrolysis in aqueous solutions is not feasible. A non- above studies.
aqueous electrolyte is suitable for aluminum electrolysis. Metal electrodeposition takes place at the
Earliest non-aqueous electrolytes developed for aluminum electrode/electrolyte interface under the influence of electric
electro-deposition at low temperatures were composed of current and includes a complex phase formation phenomena.
fused AlCl3-NaCl [1]. Many fused salts have been developed Fundamental aspects of electrodeposition of metals
for depositing aluminum [2-4]. Molten salts have high melting (electrocrystallization of metals) involve both nucleation and
point, high viscosity and are very corrosive. Electrolysis of crystal growth. Formation and growth of an electrodeposited
aluminum in various organic solutions was studied with very phase is a complex process and several models have been
little success due to problems such as low electrochemical proposed to describe the cathodic deposition of metals [19, 20].
window, low electrical conductivity, high volatility, and Nucleation mechanism has two distinct manifestations
inflammability. known as (i) instantaneous nucleation and (ii) progressive
However, ambient-temperature chloro-aluminate molten nucleation [21]. Instantaneous nucleation, when all the
salts prepared by combining AlCl3 with N-ethylpyridinium crystallites are nucleated practically at the initial period (t = 0)
chloride (EtpyCl) or N-butlypyridinium chloride (BupyCl) and thereafter they only grow irreversibly until the phase
were used for aluminum electrodeposition [5, 6]. These salts transformation is accomplished. Whereas in progressive
were of limited use because they were liquids only over a nucleation the crystallites are continuously nucleated during
small range of compositions and had a small electrochemical the process. Different types of growth mechanism after
window. Wilkes et al. [7] developed a new class of low nucleation of crystallite are summarized as: one dimensional
melting salts by combining AlCl3 with 1-methyl-3- needle like growth, two-dimensional cylindrical growth and
ethylimidazolium chloride (EmimCl). These melts have wide three-dimensional hemispherical or spherical growth.
electrochemical window and a large liquidus temperature Thirsk and Harrison [22] have reviewed the different types of
range. Electrolytic mixtures such as EmimCl-AlCl3 [8] and nucleation, growth mechanisms. They developed
EmimCl-AlCl3-benzene [9] were used for industrial aluminum mathematical relations involving current and time to explain
electroplating yielding promising results. Wu et. al. [10, 11] has these mechanisms. The current-time curves can be studied
studied reduction of aluminum and recycling of aluminum using potentiostatic and galvanostatic techniques for metal
alloys in AlCl3-1-butyl-3-methylimidazolium chloride melts electrodeposition processes.
at low temperatures. These ionic melts were also used for In the present study cyclic voltammetry and
refining aluminum based materials such as A356, A360 and chronoamperometry techniques were used to study the
Al-MMC. High purity, thick (0.2-0.5 mm) aluminum deposits nucleation and growth phenomena of aluminum deposition in
were obtained with high current densities and high cathode BmimCl + AlCl3 ionic liquid.
current efficiencies [12-14].

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Copper Mountain, Colorado
June 20-24, 2004
Symposium in Honour of Professor Lauri E. Holappa
Metal Separation Technologies III of the Helsinki University of Technology

II. EXPERIMENTAL PROCEDURE Chloroaluminate ionic liquid is composed of various ions


which are formed by the following reaction equilibria:
BmimCl (1-butyl-3-methylimidazolium chloride) was
synthesized and purified as described elsewhere [12]. AlCl3 R1R2ImCl + AlCl3 ' R1R2Im+ + [AlCl4]
(anhydrous 99.985%) was used as received with out further
purification. The electrolytic melt was prepared by slowly [AlCl4] + AlCl3 ' [Al2Cl7]
adding measured quantities of AlCl3 to bmimCl. Care was
taken to ensure that the temperature does not rise above Similar equilibrium reactions can be written with further
150C, since the mixing is exothermic reaction. Melts were addition of AlCl3 resulting in a mixture of ions such as:
prepared in a glove box under purified nitrogen and cooled AlCl4, Al2Cl7, Al3Cl10 and other higher order ions along
before beginning the experiment. with Cl and R1R2Im+. Where R1 and R2 are the alkyl
Experimental setup for electrorefining of aluminum components of ionic liquid and in the present case they are
consisted of a 50 ml Pyrex beaker fitted with a Teflon cap butyl and methyl respectively. Electrolyte with molar excess
(Figure 1a). Impure aluminum plate, copper/aluminum plate, of R1R2ImCl, i.e., [AlCl3: R1R2ImCl] < 1.0, is composed of
and pure aluminum wire were used as anode, cathode and AlCl4, Cl, and R1R2Im+ ions and is termed as basic. An
reference electrodes respectively. A constant potential was equi-molar electrolyte, i.e., [AlCl3: R1R2ImCl] = 1.0, is
applied across the electrodes using a Kepco power source. composed of AlCl4 and R1R2Im+ ions and is termed as
Since the electrolyte is moisture sensitive, an inert gas neutral. When a molar excess of AlCl3 is present, i.e., [AlCl3:
(argon/nitrogen) was introduced into the cell at a flow rate 50 R1R2ImCl] > 1.0, the mixture is termed acidic and is
ml/min throughout the experiment. The electrolyte was stirred composed of R1R2mim+, AlCl4, Al2Cl7, Al3Cl10and other
at a constant speed using a magnetic stirrer and the higher order anions [7].
temperature of the electrolyte was controlled by a hot plate. Refining of aluminum alloys in chloroaluminate ionic
All the experiments were carried out under a vacuum hood liquids takes place by the dissolution of aluminum from alloy
and at 105 5C. anode by ions present in the electrolyte and deposition at the
Electrochemical studies were performed using a three cathode. The mechanism of aluminum electro-refining in
electrode electrochemical cell (Figure 1b). The reference BmimCl-AlCl3 electrolyte is presented systematically in the
electrode (RE) and counter electrode (CE) were made of high form of electrode reactions. The anode-dissolution reaction
purity aluminum wire with outer diameter ( = 1.5 mm). The and deposition at cathode are given by equations (1) and (2)
working electrode (WE) was a copper wire ( = 1.25 mm) respectively.
with the active surface area determined from length of the
electrode immersed into electrolyte. The reference electrode Al (anode) + 7 AlCl4 = 4 Al2Cl7 + 3e
(1)
consisted of aluminum wire immersed in Pyrex capillary glass
tube filled with the same electrolyte. The reference electrode 4 Al2Cl7 + 3e = Al (cathode) + 7 AlCl4
was kept close to the working electrode so that the solution (2)
resistance can be neglected. Electrochemical experiments
were performed using an EG&G PARC model 273A Aluminum electro-refining is feasible only in acidic
Potentiostat/Galvanostat. electrolytes due to the presence of Al2Cl7which is essential
for aluminum deposition reaction (Eq. 2). Dissolution of
+ Potentiostat aluminum depends on anode potential and kinetic aspects of
Reference
electrode
the electrolyte-electrode system such as ohmic potential,
Thermometer
Inert Gas Inert
concentration polarization and activation polarization.
Inert gas
inlet outlet inlet Inert
outlet Impurities such as Si, Cu, and Zn present in the anode, which
Anode Auxiliary have lower reduction potential than that of aluminum will not
(Al-MMC)
dissolve since the acidic electrolyte does not contain free Cl
Electrode Working
(Al) Electrode
Cathode Electrolyte Glass
(Cu)
ions.
(Pure
copper Electrolyte
Reference
Electrode
Constant voltage electrolysis was performed for
Temperature bath
Stirrer III
(Al/ Al ) electrorefining aluminum alloys. Current output was noted at
Porous frit regularly intervals and was converted into current density by
(a) (b) dividing it with cross sectional area of electrode immersed in
Figure 1. Experimental setup for (a) electro-refining and (b) electrolyte. The reported current densities are based on
electrochemical studies. cathode area measured after electrolysis. Thickness of
deposited aluminum varied from 0.20.6 mm for planar
deposits and from 0.40.9 mm for dendritic deposits.
III. RESULTS AND DISCUSSION Impurities such as Si, Cu, Zn etc., either remain on anode or
settle to the bottom of cell as anode sludge. Compositional
A. Electrorefining of Aluminum analysis of aluminum anode obtained from mass spectrometer
analysis is: Al: 79.77, Si: 11.62, Fe: 0.76, Mn: 0.19, Mg: 0.06,
Aluminum alloys (A360 and A356) were electrorefined Cu: 5.00, Ni: 0.08, Zn: 2.32, Pb: 0.07 Wt %. After
using ionic liquid electrolyte. Electrolyte consisted of a electrolysis, deposits are cleaned with acetone and water to
mixture of AlCl3 and BmimCl in the molar ratio 1.5-2.0: 1.0. remove any organic impurities adhered to electrode. Unless

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Copper Mountain, Colorado
June 20-24, 2004
Symposium in Honour of Professor Lauri E. Holappa
Metal Separation Technologies III of the Helsinki University of Technology

specified all electrolysis experiments were performed for a characteristic segments are seen in Figure 2. First segment
period of 2 hours. (region A), current density increases rapidly for a short time
Current efficiency of the process was determined form the followed by a steady state increase in the transition phase
amount of metal deposited by passage of fixed quantity (region B), and finally in region C, it attains a saturation limit.
electric charge. Moreover the amount of metal deposited was Rapid increase of current density in region (A) was due to
estimated from weight change (W) observed in cathode. activation polarization at cathode [12, 23]. Similar current
Using Faraday law, the theoretical amount of metal to be density vs. time plots were obtained at other voltages and
deposited for a fixed quantity of electricity passed was concentrations of electrolyte studied in the present study [12].
determined:

I t Am (3) B. Effect of Cell Voltage


Wm =
nF
The effect of cell voltage on current density and cathode
where Wm is theoretical amount of metal deposited, I t current efficiency of electrorefining process was studied by
(current time) is quantity of electricity supplied, n is number varying applied voltage from 1.0 to 1.6V and at constant
of electrons transferred, Am is atomic of metal and F is concentration ratio (AlCl3/BMIC) of CR=1.5. Figure 3 shows
Faraday constant (96485 Coulombs). Current efficiency (eff), the variation of current density as a function of applied cell
which is defined as the ratio of the actual amount of metal voltage. Current density is observed to increases with
deposited to that expected theoretically was calculated. increasing voltage at fixed composition of electrolyte. With
increasing voltage the rate of discharge (reduction) at cathode
Actual amount of metal deposited (W) is enhanced and thereby current density rises.
eff = Figure 3 shows the effect of applied cell voltage on cathode
Theoretical amount of metal deposited (Wm ) (4) current efficiency for A360 alloy at constant electrolyte
composition (CR=1.5) and temperature (1055C). Cathodic
Energy consumed (E) during electrorefining process was current efficiency was observed to be well above 98% at all
determined from the following relation (Eq. 5): the applied voltages. High current efficiencies indicate no side
reactions other than deposition of aluminum at cathode.
Q Similar results were obtained at other concentrations of
E = V
electrolyte (CR = 1.6, and 1.8).
eff (5)
400
where V is the applied cell voltage, eff is cathode current 100

efficiency, and Q is theoretical charge required for depositing


2
Average Current Density, A/m

Cathode Current Efficiency, %


350 80
a fixed amount of material (Faradays law). Energy
consumption estimated for the process at 1.0V applied voltage 300 60
was about 3.0 kWh/kgAl. As the cell voltage increased the
energy consumption also increased giving an optimum value 250 40
at 1.0V [12].
200 20

C
500
150 0
B 1.0 1.1 1.2 1.3 1.4 1.5 1.6
400 Voltage, V
2
Current Density, A/m

300
Figure 3. Variation of current density and cathode current
200 efficiency with applied cell voltage at CR=1.5, 1055C.
A

100
Effect of applied voltage on morphology of the aluminum
deposits is shown in Figure 4. Figure 4 shows the SEM
0
0 20 40 60 80 100 120 micrographs of aluminum deposits at applied voltages (1.0,
Time, min 1.3, and 1.5V) at CR = 1.5 and 1055 C. At low voltages
clustering of particles is seen since, discharge of ions is low
Figure 2. Variation of current density with time at different and growth rate is higher than the nucleation rate at low
applied voltages, CR = 1.5, V = 1.5V and 1055C. current densities. However as voltage increases, nucleation
rate increases and deposits is finer with large number of
During electrolysis cathodic current density increased with nuclei. Thus higher applied voltages produce uniform particle
time and typical current density vs. time plots are shown in size distribution and uniform thickness of the deposit. Similar
Figure 2. The curves shown in Figure 2, were obtained at a microstructural observations were seen at the other
concentration ratio of electrolyte (CR=1.5) and 1055C for concentrations of electrolyte (CR = 1.6, and 1.8).
different applied voltages (1.0-1.5V). Distinctly three

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Copper Mountain, Colorado
June 20-24, 2004
Symposium in Honour of Professor Lauri E. Holappa
Metal Separation Technologies III of the Helsinki University of Technology

(a) (b) at cathode is considerable. The decrease in concentration of


reducible ions increases cathodic polarization and growth rate
of the metal deposit is thus reduced. On increasing the
concentration, cathodic polarization decreases due to decrease
in thickness of diffusion layer at cathode. An increase in
concentration of ions at cathode by diffusion favors growth of
existing layer of deposit resulting in formation of large grains.
Thus, at low concentrations of electrolyte uniform particle
size distribution with a uniform thickness of the deposit was
(c) obtained.

(a) (b)

Figure 4. Microstructures of aluminum deposited at voltages


(a) 1.0, (b) 1.3V, (c) 1.5V, CR=1.5 and 1055C [12].
(c)

C. Effect of Electrolyte Composition

Composition of electrolyte plays an important role in most


electrorefining processes. As mentioned previously
composition of AlCl3 in melts determines properties of the
electrolyte. Figure 5 shows the effect of electrolyte
composition on current density at an applied voltages of 1.6V
and constant temperature 1055C. However, no significant Figure 6. SEM micrographs showing microstructure of Al
variation in current density was observed with increasing deposits obtained at different concentration of electrolyte (a)
composition of AlCl3. This indicates that with 1.0, (b) 1.5, (c) 1.8 and V =1.5, 1055C [12].

400 100
D. Effect of Temperature
Cathode Current Efficiency, %

350
2
Average Current Density, A/m

80

300
Effect of temperature on electrorefining process was studied
60 by varying the temperatures from 75 to 125C. Figure 7
250 shows the variation in current density as a function of
40 temperature at an applied cell voltage of 1.5V and CR=1.5.
200
Current density was observed to increase approximately
150
20 linearly as the temperature rose from 75 to 125C. At higher
temperatures the rate of diffusion of reducible ions to cathode
100
1.50 1.55 1.60 1.65 1.70 1.75 1.80
0 is enhanced and consequently current density rises. Moreover
Concentration Ratio, CR at high temperatures concentration polarization is also
reduced.
Temperature affects physical properties such as viscosity
Figure 5. Effect of electrolyte composition on current density and density of electrolyte. Viscosity and density of these
and cathode current efficiency at 1055C, and V = 1.6V. melts decreases with increasing temperatures for the range of
compositions of electrolyte used in this study [24]. Lower
Figure 5 shows the influence of electrolyte composition on viscosity improves the mobility of ions and hence higher
cathode current efficiency at an applied cell voltage of 1.6V current densities are observed at high temperatures.
and 1055C. Cathode current efficiency was found to be The variation of cathode current efficiency as a function of
well above 90% with increasing CR. As mentioned earlier temperature was studied at different applied cell voltages (1.0,
high current efficiencies are indication of no side reactions. 1.3, and 1.5V) and fixed electrolyte composition (CR=1.5) is
Similar results were obtained at other voltages 1.0V and 1.3V. shown in Figure 7. Cathode current efficiency remained
Figure 6 shows the SEM micrographs of aluminum deposits above 95% within the range of experimental temperatures
at different concentration ratios (CR= 1.0, 1.5 and 1.8), (75125C). Sim ilar results were obtained at other voltages
applied cell voltage of 1.5V and 1055 C. At low 1.0V and 1.3V.
concentrations of reducible ions, depletion in diffusion layer

146
Copper Mountain, Colorado
June 20-24, 2004
Symposium in Honour of Professor Lauri E. Holappa
Metal Separation Technologies III of the Helsinki University of Technology

potential to initial potential and thus a full cycle is completed.


400 100
The range between initial and switching potential is so chosen
375
that all possible electrochemical reactions are observed. This
2

Cathode Current Efficiency, %


Average Current Density, A/m 350 80
range usually corresponds to electrochemical window of
325
60
electrolyte.
300 Figure 9 shows the typical cyclic voltammogram obtained
275 40
for aluminum deposition on copper electrode. Two significant
250
peaks one in negative region and other in positive region can
225
20 be observed. Negative peak corresponds to cathodic reduction
reaction (Al deposition) and positive peak is anodic oxidation
200
0 reaction (Al stripping). Anodic peak current (peak height)
70 80 90 100 110 120 130

exceeds that of cathodic peak (Ia >Ic). Also the peak areas are
Temperature, C
different and the separation between peaks is large.
Asymmetric peak areas and large peak separation is an
Figure 7. Effect of temperature on current density and cathode indication that the aluminum deposition process is quasi-
current efficiency at CR=1.5 and V = 1.5V. reversible [25]. Quasi-reversible means both the forward and
reverse reactions take place but are not fast enough to be
Aluminum deposit microstructure was studied at different considered to be at equilibrium [26].
temperatures and a fine grained deposit was obtained at Charge transfer coefficient which is a measure of
intermediate temperature of 105C. reversibility of reaction is determined from the peak
potentials. From Figure 9, the value of |Ep-Ep/2| (where Ep and
2500
Al Ep/2 are cathodic peak and half-peak potentials respectively)
was found to be considerably larger than that expected for
2000
reversible process involving multiple electron transfer.
Intensity, cps

1500

Al E p E p / 2 = 1.857 RT nF
1000 (6)
Al Al
500
Al
The relation between charge transfer coefficient () and
peak potentials for an irreversible process is given by Eq. (6)
0 [23]
20 40 60 80 . Since aluminum deposition in the present process is
2 quasi-reversible, above relation was used to determine charge
transfer coefficient and an average value of 0.4 was obtained.
Figure 8. X-ray diffraction pattern of the aluminum deposits.

An XRD pattern of aluminum deposit is shown in Figure 8. 30

From XRD analysis it was determined that aluminum deposits = 8 mV/s


20
were of high purity. Further composition analysis of the Anodic Ia
Current (mA)

deposits was performed using mass spectrometer, Al: 99.89, 10


Fe: 0.03, Cu: 0.03, Zn: 0.03 and Ni: 0.01 Wt%.
0

-10
E. Electrochemical Studies Cathodic Ic
-20
-2 -1 0 1
Electrochemical studies on ionic liquids were carried out to Voltage (V) vs. Al / Al(III)
characterize liquids and to investigate the behavior of
electrolyte at electrode interface. Electrochemical studies
Figure 9. Cyclic voltammogram for aluminum deposition on
were performed using controlled potential methods, namely
copper substrate in AlCl3: BMIC (1.5:1.0) electrolyte at 30C.
cyclic voltammetry (CV) and chronoaperometry (CA).
Voltammograms were recorded at different scan rates
ranging from 0.06 to 0.5V/s with copper as working
a. Cyclic Voltammetry
electrode. Figure 10 shows the voltammograms at low scan
rates in the range of 0.13-0.35V/s. Both cathodic and anodic
In cyclic voltammetry a stationary planar disk working
peaks have shifted with increasing scan rate. Cathodic peaks
electrode is placed in an unstirred solution. The working
have shifted towards more negative potentials. Whereas, the
electrode is then set to an initial potential where the
anodic peaks have shifted towards positive direction. The
electrochemically active species is not electrolyzed and the
shift in peak potentials with scan rate indicates the irreversible
potential is changed at a constant rate (scan rate ) to a nature of the process. The reversibility of a process is
potential called switching potential. This is the onward cycle quantitatively measured from the value of charge transfer
and in reverse cycle the potential is reversed from switching

147
Copper Mountain, Colorado
June 20-24, 2004
Symposium in Honour of Professor Lauri E. Holappa
Metal Separation Technologies III of the Helsinki University of Technology

coefficient (). The charge transfer coefficient for a Although equation (7) shows that the plot of Ip vs. 1/2 must
completely reversible process is 0.5 and for a quasi-reversible pass through origin, a non-zero intercept is seen in the present
process = 0.3-0.7 [23]. study. The positive intercept seen in figure 11 indicates a
Another prominent feature noticed from Figure 10 was that deviation from assumption that the diffusion controlled
the peak current changed with scan rate. Increasing the scan process was linear [19]. Deviation from linear diffusion may be
rate is equivalent to increasing the rate of diffusion and results due to (i) adsorption of reaction products on electrode or (ii)
in an increase in peak current. A relation between peak due to non-planar geometry of electrode. In case of spherical
current (Ip) and scan rate () for a quasi-reversible process or cylindrical electrode (present study) semi-infinite diffusion
assuming linear diffusion is given by Eq. (7) [23]. could be possible [19, 23].

I p = 0.4958n 3 / 2 AC 0* D01 / 2 1 / 2 F 3 RT ( )1/ 2


(7)
b. Chronoamperometry

where n (=3/4) is the number of electrons involved in rate Chronoamperometry is the study of current response as a
determining step, F faradays constant, Do is diffusion function of time when a potential step to cause an
coefficient of electroactive species, Co* is bulk concentration electrochemical reaction is applied to an electrode.
in moles/cm3 and A is area of electrode and other variables Chronoamperometry can be used for determine diffusion
have their usual meaning. Thus a linear relation between peak coefficients, and investigating kinetics and nucleation
current and scan rate is typical for a diffusion controlled mechanism. A single CA can give much more information
reaction. than a CV; however multiple CA experiments were
performed to further characterize the electrolyte.
40

30 0.35
0.25 20
20 0.18
Current (mA)

0.13
10 15 -0.5V

Current (mA)
10
-10 -0.4V

-20
5 -0.3V
-2 -1 0 1
-0.2V
Voltage (V) vs. Al/Al(III) 0 -0.1V

Figure 10. Voltammograms for aluminum deposition at -1 0 1 2 3


different scan rates (V/s). Time (sec)

Figure 11 shows the variation of peak current (Ip) as a


function of square root of scan rate (1/2). A linear plot Figure 12. Chronoamperometric I vs. t transients for Al
indicates a diffusion-controlled process at cathode. Diffusion deposition at different over-potentials indicated in figure.
coefficient of the electro-active species, Al2Cl7 can be
calculated from Eq. (7) was found to be Do=1.13107 Chronoamperometric current-time transients on copper
cm2/sec. working electrode in the current electrolyte (AlCl3: BMIC =
1.5: 1.0) are shown in Figure 12. Several CA curves were
obtained by varying the step potential as shown in Figure 12.
0.025
During metal deposition, metal ions at electrode surface get
reduced and solution is depleted of the ions. Thus a diffusion
0.020
gradient at the electrode surface is developed and further
reaction takes place only by diffusion of ions from bulk.
Ip (mA)

0.015 Hence when a potential step is applied, the current rises


initially as the electroactive area increases, either by growth
0.010 of individual nuclei in size or by increasing number of nuclei
[27]
.
0.005 During this stage of growth of deposit, nuclei develop
0.2 0.3 0.4 0.5 0.6 0.7 hemispherical diffusion zones around themselves. And when
1/2 (mV/sec)1/2 these zones overlap, hemispherical mass transfer gives way to
linear mass-transfer, i.e., diffusion perpendicular to an
effectively planar surface [28, 29]. Accordingly, the current
Figure 11. Variation of peak current (Ip) as a function of scan passes through a maximum value and then decreases rapidly
rate (1/2), area of working electrode: 0.68 cm2. to a steady state current as seen in Figure 12.
Cottrells relation can be used to describe the decreasing
portion of current-time transients shown in Figure 12.

148
Copper Mountain, Colorado
June 20-24, 2004
Symposium in Honour of Professor Lauri E. Holappa
Metal Separation Technologies III of the Helsinki University of Technology

Cottrells equation for a simple diffusion controlled process is implies that number of available nucleation sites is potential
given in Eq. 8. The terms in Eq. 8 are: I is current in Ampere, dependent.
nF is molar charge, A is area of electrode, Co* is bulk A further analysis of chronoamperometric current-time
concentration, t is time and Do is diffusion coefficient of transients was done to establish the type of nucleation. The
electroactive species. dimensionless current-time relations for two types of
nucleation are given in Eqns. (11) and (12) [28]. These
I = nFAD0
1/ 2
C 0* (t ) 1 / 2 (8) dimensionless current-time relations applicable for diffusion
controlled three-dimensional progressive and instantaneous
nucleation respectively.
18
20
15 18

16
12
14
Current, mA

9 12

I, mA
10
6 8

6
3
4

0 2
0.0 0.4 0.8 1.2 1.6 2.0
0
1/2 0.5 0.0 0.2 0.4 0.6 0.8 1.0
t , sec
1/2 0.5
t , sec

Figure 13. Variation of current (I) as a function of time (t 1/2)


for the decreasing portion of I vs. t, transients (0.5V) shown in Figure 14. Variation of current (I) as a function of time (t )
Figure 12. for rising portion of I vs. t, transients, () 0.2V, (U) 0.3V,
() 0.4V, (V) 0.5V over-potentials shown in Figure 12.
Cottrells equation can be applied to the decreasing portion
of the transients in Figure 12 by plotting I vs. t1/2. The linear
(i im )2 = 1.2254(t tm )1 (1 exp[ 2.3367(t tm )2 ])
2
(11)
relationship I t1/2 is typical for a diffusion-controlled
process under uniform conditions of linear diffusion [30]. The
linear relationship seen in Figure 13 indicates that the 1.20

electrodeposition of aluminum is diffusion-controlled process. 1.00


The diffusion coefficient calculated from the slope of straight 0.80
line in Figure 13 is Do = 0.6310 7 cm2 /s.
[ i / i m ]2

Astley et. al., [31] have derived current-time relationship to 0.60

describe the growth of three-dimensional hemi-spherical 0.40

nuclei under diffusion controlled conditions. Assuming linear 0.20

diffusion the current-time relation for the growth of No nuclei 0.00


already present or formed instantaneously is given by Eq. (9) -0.20
and corresponding expression for progressive growth of 0 1 2 3 4 5

nuclei is given by Eq. (10). [t / t m ]

I = 8 N o zFM 2 (Co* )3 Do3 / 2t1 / 2 2 1 / 2 (9) Figure 15. Dimensionless (i/im)2 vs. t/tm, plots for I vs. t,
transients obtained at over-potentials: () 0.5V, () 0.6V, ()
I = 16kn N o zFM 2C 3 D 3 / 2t 3 / 2 (3 2 1 / 2 ) 1 (10) 0.7V, () 0.8V, and () instantaneous, (----) progressive
nucleation theoretical models.
where M is molecular weight, is density of metal, Co and Do
are the concentration and diffusion of the electroactive
(i im )2 = 1.9542(t tm )1 (1 exp[ 1.2564(t tm )])2 (12)
species, t is time, kn is the rate constant for formation of
nuclei and other terms have their usual meaning. where i, im are current density, maximum current density
Figure 14 shows I vs. t1/2 plots for rising portions of the (A/cm2) and t, tm are time, maximum time (sec) respectively,
transients in figure 12. A linear relation (It1/2) was observed obtained from the current-time transients in Figure 12.
at all the over-potentials shown in Figure 14. Thus indicating Figure 15 shows the dimensionless current-time plots for
that aluminum deposition process in these ionic melts is an over-potentials ranging from 0.5 to 0.8V and two theoretical
instantaneous three-dimensional nucleation. Moreover, the curves corresponding to instantaneous and progressive
growth following nucleation is controlled by diffusion of nucleation. Experimental curves closely followed the
chloroaluminate (Al2Cl7) ions as confirmed previously. The instantaneous type of nucleation with slight deviation at
marked dependence of growth current on over-potential t/tm<1 and at higher time periods. However, at low

149
Copper Mountain, Colorado
June 20-24, 2004
Symposium in Honour of Professor Lauri E. Holappa
Metal Separation Technologies III of the Helsinki University of Technology

overpotentials below 0.5V, the dimensionless current-time VII. REFERENCES


plots are positioned in between the progressive and
instantaneous type of nucleation indicating that nucleation is 1. Bunsen: Poggendorrfs Ann., vol.97(1854) pp.648.
2. Fink, C. G. and Solenki, D. N.: Trans. Electrochem. Soc., vol.91, (1947)
potential dependent. Clearly, aluminum deposition in ionic pp.203.
melts involves instantaneous nucleation with diffusion- 3. Kroll, W. J.: Trans. Electrochem. Soc., vol.87 (1945) pp. 551.
controlled growth of three-dimensional centers as reported in 4. Peled, E. and Gileadi, E.: The Electrodeposition of Aluminum from
literature [25]. Aromatic Hydrocarbon, J. Electrochem. Soc., vol.123 (1976) pp.15-19.
5. Wier, T. P. and Hurley, F. H.: Electrodeposition of Metals from Fused
Treatment of the chronoamperograms discussed above Quaternary Ammonium Salts, Journal of Electrochemical Society,
requires that the product (im2tm) be independent of the vol.98 (1951) pp. 203-206.
nucleation and growth rates, i.e., over-potentials. Thus at a 6. Wier, T. P. and Hurley, F. H.: The Electrodeposition of Aluminum
given bulk concentration of electrodepositing species im2tm from Nonaqueous Solutions at Room Temperature, Journal of
Electrochemical Society, vol.98 (1951) pp. 207-212.
should not vary with over-potential for sufficiently high step 7. Wilkes, J. S., Levisky, J. A., and Hussey, C. L.: Dialkylimidazolium
potentials, for which the surface concentration of aluminum is chloroaluminate melts: A New Class of Room Temperature Ionic
effectively zero. Liquids for Electrochemistry, Spectroscopy and Synthesis, Inorganic
Chemistry, vol.21 (1982) pp. 1263-1265.

( )2 8. C. L. Hussey: Advances in Molten Salt Chemistry, Ed. Mamantov, G.,


im2 t m = 0.1629 nFC0 D0 (13) Amsterdam, Elsevier Science (1983) Vol. 5, pp. 185.
9. R. A. Osteryoung: Molten Salt Chemistry, Eds. Mamantov, G. and
Marassi, R., Holland, D. Reidel (1987) 329.
Moreover, diffusion coefficient of Al2Cl7 ions was 10. Wu, B., Reddy, R. G., and Rogers, R. D.: Aluminum Reduction via
calculated from the maxima in the current-time transients Near Room Temperature Electrolysis in Ionic Liquids, Light Metals
using Eq. (13), which is developed for instantaneous type of 2001, Ed. Anjier, J. L., Warrendale, PA, TMS (2001) pp. 237-243.
nucleation [29]. From the mean value of the product im2 tm = 11. Wu, B., Reddy, R. G., and Rogers, R. D.: Aluminum Recycling via
Near Room Temperature Electrolysis in Ionic Liquids, Fourth
6.48 x 105 A2 s /cm4, resulting from experimental CA International Symposium on Recycling of metals and Engineered
exhibited in Figure 12, diffusion coefficient was obtained as Materials, Eds. Stewart, Jr, D. L., Daley, J. C., and Stephens, R. L.,
Do = 3.9 x 107 cm2 sec1. The diffusion coefficients obtained Warrendale, PA, TMS (2000) pp. 845-856.
in the present study are comparable to that available for 12. Kamavaram, V., Mantha, D., and Reddy, R. G., Electrorefining of
Aluminum Alloy in Ionic Liquids at Low Temperatures, Journal of
aluminum deposition in the literature. Mining and Metallurgy B, vol.39 (1-2) (2003) pp. 43-58.
13. Kamavaram, V. and Reddy, R. G., Recycling of Aluminum Based
Materials in Ionic Liquids, Recycling and Waste Treatment in Mineral
IV. CONCLUSIONS and Metal Processing: Technical and Economic Aspects Proceedings,
Eds. B. Bjorkman, C. Samuelson, and J. O. Wikstrom, , Warrendale,
PA, TMS; MEFOS, Lula, Sweden, vol. 2 (2002) pp. 517-526,.
Aluminum alloy (A360) was electrorefined in an acidic 14. Kamavaram, V. and Reddy, R. G., Recycling of Al-MMC in Ionic
mixture of anhydrous aluminum chloride and 1-butyl-3- Liquids at Near Room Temperature, ICCE/9, Proceedings of
methylimidazolium chloride. High purity aluminum (99.89%) International Conference on Composites Engineering, Ed. Hui, D.,
University of New Orleans, LA, (2002) pp. 359-360.
was obtained. High voltages and temperatures lead to higher 15. Schulze, K. and Hoff, H., Electrode Kinetics of Aluminum in Chloride
current densities and current efficiencies. However Melts with Respect to Electrocrystallization, Electrochimica Acta,
compositions of the electrolyte had no-significant effect on vol.17 (1972) pp.119-133.
either current densities or current efficiencies. A major 16. Lefebvre, M. C., and Conway, B. E.: Elementary Steps and
Mechanism of Electrodepostion of Al from Complex Hydride ions in
advantage of the present process is its low energy Tetrahydrofuran Baths, Journal of Electroanalytical Chemistry,
consumption of about 3.0 kWh/kgAl, compared to 1718 vol.480 (2000) pp. 34-45.
kWh/kg-Al for the existing industrial refining process. 17. Legrand, L., Trenchant, A. and Messina, R.: Electrodeposition Studies
Initial stage of electrodeposition of aluminum in ionic of Aluminum on Tungsten Electrode from DMSO2 Electrolyte,
Journal of Electrochemical Society, vol.141 (1994) pp. 378-382.
liquids was found to be quasi-reversible, with the charge 18. Carlin, R. T., Crawford, W., and Bersch, M.: Nucleation and
transfer coefficient = 0.40. Aluminum deposition on copper Morphology Studies of Aluminum Deposition from an Ambient
in AlCl3-BmimCl electrolyte was found to be instantaneous Temperature Chloroaluminate Molten Salt, Journal of Electrochemical
nucleation followed by diffusion controlled three-dimensional Society, vol.139 (1992) pp. 2720-2727.
19. Hill, G. J., Schiffrin, D. J. and Thompson, J.: Electrochemical
growth of nuclei. Diffusion coefficient of the electroactive Nucleation from Molten SaltsI. Diffusion Controlled Electrodeposition
species (Al2Cl7) calculated from cyclic voltammetry of Silver from Alkali Molten Nitrates, Electrochimica. Acta, vol.
(Do=6.5107 cm2s1) and chronoamperometry (Do=3.9107 19(1974) pp. 657-670.
cm2sec1) are comparable with that reported for aluminum 20. Fleischmann, M. and Thrisk, H. R.: Advances in Electrochemistry and
Electrochemical Engineering, Vol. 3, Eds. Delahay, P. and Toibas, C.
deposition in the literature. W., New York, Interscience, (1963).
21. Kashchiev, D.: Nucleation: basic theory with applications, Heinemann,
MA, Butterworth (2000).
VI. ACKNOWLEDGEMENTS 22. Thrisk, H. R. and Harrison, J. A.: A Guide to the Study of Electrode
Kinetics, New York, Academic Press (1972) pp. 115-135.
23. Bard, A. J. and Faulkner, L. R.: Electrochemical Methods:
Authors would like to acknowledge the financial support for Fundamentals and Applications, New York, J. Wiley & Sons, Inc.
present research by the following organizations: National (2000) pp. 235-236, 242.
Science Foundation (NSF), Department of Energy (DOE) and 24. Kamavaram, V. and Reddy, R. G.: Physical and Thermal Properties of
Ionic Liquids Used in Aluminum Electrorefining at Low
The University of Alabama (UA). Temperatures, Aluminum 2003, Ed. Das, S. K., Warrendale, PA, TMS
(2003) pp. 299-307.

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Copper Mountain, Colorado
June 20-24, 2004
Symposium in Honour of Professor Lauri E. Holappa
Metal Separation Technologies III of the Helsinki University of Technology

25. Zhao, Y. and Vandernoot, T. J.: Electrodeposition of Aluminum from


Room Temperature AlCl3TMPAC Molten Salts, Electrochimica.
Acta, vol.42 (1997) pp. 1639-1643.
26. Grosser, Jr., D. K.: Cyclic Voltammtery Simulation and Analysis of
Reaction Mechanisms, Florida, VCH Publishers Inc. (1993).
27. Gunawardena, G. A., Hill, G. J. and Montenegro, I.: Potentiostatic
Studies of Electrochemical Nucleation, Electrochimica. Acta, vol.23
(1978) pp. 693-697.
28. Scharifker, B. and Hill, G.: Theoretical and Experimental Studies of
Multiple Nucleation, Electrochimica. Acta, vol. 28 (1983) pp. 879-
889.
29. Gunawardena, G. A., Hill, G. J., Montenegro, I. and Scarifker, B.:
Electrochemical Nucleation: Part I. General Considerations Journal
of Electroanalytical Chemistry, vol.138 (1982) pp. 225-239.
30. Delahay, P.: New Instrumental Methods in Electrochemistry, New
York, Interscience, (1954) chapter 3.
31. Astley, D. J., Harrison, J. A. and Thirsk, H. R.: Electrocrystallization
of Mercury, Silver and Palladium, Trans Faraday. Soc, vol. 64 (1968)
pp. 192-201.

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