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Holappa
Metal Separation Technologies III of the Helsinki University of Technology
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.
143
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
144
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:
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)
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
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.
-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
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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
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].
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
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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
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
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
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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
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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
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Copper Mountain, Colorado
June 20-24, 2004