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Electrochemical Engineering
for Commodity Metals Extraction
by Antoine Allanore

W
ith the projected addition of 2 billion inhabitants on It is acknowledged that the existing technologies operate close
earth by 2050, the primary extraction of commodity to the thermodynamic minimum, with a total energy consumed
metals is poised to grow. For comparison, the of around 5000 kWh/t and an equivalent CO2 emission of around
population increase of nearly 2 billion over the last 1.85 tCO2/t. This energy originates mostly from coal and is partly
35 years led to a doubling of the primary production used in the numerous steps necessary before and after the blast-
of iron (Fe) and copper (Cu), while aluminum (Al) production almost furnace (coke and sinter production, conversion to steel).To date
tripled. Figure 1 shows the production of key metals by tonnage in there are no electrolytic processes to substitute C-based extraction
2015.1-4 Within the next 33 years, the metal industry will not only of Fe, in part because of the multiple valency of iron (Fe3+ and Fe2+),
need to increase its output, but equally important, deliver those and the stringent economics and scale of this metal production. At
metals at a cost affordable to the regions experiencing the greatest conversion costs of less than $350/t6 for a product that often sells for
population growth. Indeed, for various logistical and economic less than $500, the room for operational uncertainty and inefficiency
reasons, those regions today have access to those metals only at is very limited.
prices that exceed global trade prices. Meanwhile, environmental (continued on next page)
awareness, both globally (e.g., greenhouse gases) and locally (e.g.,
SOx, dioxines, dusts emissions, or water consumption), calls for a
significant technological effort to enhance the sustainability of these million tonnes $ billion
industries.5 Is it possible that cost effective, C-free power generation in 2015 in 2015
put forth in several energy scenarios enable the metal extraction
industries to revisit their technologies? In a future with GHG-free
electricity at potentially $0.05 per kWh, could electrochemical
engineers dedicated to Fe, Al, or Cu primary production offer a
sustainable path? In particular, which electrolyte could enable us to
match the productivity of today’s technology? An overview of the
present markets and underlying technologies is presented in this
article to help frame the discussion.

Situation in 2015
Fig. 1. Left, global production of primary Fe, Al, Cu, and Zn+Pb in 2015,
Market Reality in million tons. Right shows estimates of the corresponding mining market
As presented in Fig. 1, the metal most consumed is iron (Fe), revenue used as feedstock today (Fe2O3@$60/t, Al2O3@$350/t, Cu, Zn,
mostly in the form of steel products, with 1,620 million tons and Pb feedstocks are sulfides, accounted here as metal value contained in
produced in 2015 (equivalent to almost one Eiffel tower every 2 concentrates3,4).
minutes). Second is aluminum at 60 million tons followed by copper
at 18 million tons. Zinc and lead are next, together at around 24
million. The demand for these primary metals drives the mining of
the corresponding ores and the production of concentrates, whose
market shares are summarized in Fig. 1. The revenue from mining
metal feedstocks represents several hundred billion dollars per year,
not counting gold and silver, with oxides (for Fe, Al, but also Mn, V,
Cr, Ti, etc.) and sulfides (for Cu, Zn, Pb, but also Ni, Ag, etc.) equally
represented. Figure 2 shows the energy, metal price and conversion
costs that support the annual consumption rates shown in Fig. 1. At
around $5000/t ($2.3/lb), copper is barely sold at the retail price of
organic potatoes in North America. Around 10 times less expensive
($0.25/lb), steel is sold at less than the retail price of flour. These
prices are an essential reality of commodity production, and it is hard
to conceive developing countries being able to cope with higher costs
for those products in the future.

Energy, Costs and Environment

Figure 2 also shows the amount of energy consumed for the
extraction of one tonne of metal today. A summary of the underlying
engineering principles, technical progress, and role of electricity can
be read elsewhere10 for iron. The chemical basis of its extraction is
the carbo-thermic reduction of iron oxide (Fe2O3, >90% ) following
Eq. 1, conducted in a blast-furnace where liquid iron (pig iron) is
produced:
Fig. 2. Specific energy consumption (bars) and conversion costs (dots, x10).
Fe2O3 + 3 2 C → 2 Fe(l ) + 3 2 CO2 ( g ) (1) Price estimates are shown in parenthesis. Data for conversion costs: Fe from
Ref. 6, Al from Ref. 7 and 8, and Cu from Ref. 9.

The Electrochemical Society Interface • Summer 2017 • www.electrochem.org 63

Allanore
(continued from previous page)
For copper, the chemical extraction from sulfides represents 80%
of the primary copper produced yearly,9 and is based on the simplified
Eq. 2 which produces liquid copper, liquid oxide (slag) and sulfur
dioxide (to be converted to sulfuric acid):
(Cu , Fe) S 2 + 5 2 O2 ( g ) → Cu (l ) + FeO(l ) +
= 2 SO2 ( g )
Here, despite the exergonic nature of Eq. 2 predicted by
thermodynamics, the actual net energy consumption is around
3600 kWh/t, with nearly 70% of it being electricity consumption.11
Per se, the copper production from sulfide today has room to
improve its energy efficiency. Some of the reasons for such energy
consumption are the need to prepare nearly pure O2 from air, the
need to recover part of the copper oxide contained in the FeO in an
electric arc furnace, and the need to convert SO2 into sulfuric acid.
Additional refining of the liquid Cu are also needed to obtain copper
of sufficient purity (electrorefining, 340 kWh/t12). While several
electrolytic processes have been proposed to substitute the existing
smelting operation, a cost-competitive substitute to directly make
liquid copper from sulfide ores solely based on electrochemistry has
yet to be found. The selectivity for the various elements present in
copper sulfide concentrates is a key challenge to current practices, as
exemplified by the amount of Fe lost as FeO (almost 1 tFe/tCu), or the
difficulty in the direct recovery of elements more noble than Cu such
as Ag, Mo, or Sb. Conversion costs are estimated at $320 per ton of
copper, including $100 per ton for electrorefining.9 Interestingly, the
conversion costs for Cu are very similar to those for Fe, and both
processes rely on pyrometallurgy, oxidation of a fuel (S for Cu, C for
Fe), and gas/liquid or gas/solid reactions.
Liquid aluminum is produced from high purity alumina (Al2O3,
+99.5%) using both carbon affinity for oxygen and electrolysis,
since Eq. 3 is driven and maintained at temperature solely thanks to
electricity:
Al2O3 + 3 2 C → 2 Al (l ) + 3 2 CO2 ( g )
As reviewed in this journal,13 the efficiency of the Hall-Héroult
(HH) electrolysis process underlies the affordability of aluminum,
and remains the hallmark of primary metal extraction by electrolysis.
It is presented in some details hereafter since it may serve as a
baseline for the deployment of novel electrolytic processes for direct
decomposition of other metal compounds, such as Fe2O3 for iron or
CuFeS2 for copper. The process today for aluminum14 consumes a
carbon anode (0.4 tC/t) and around 13,000 kWh/t for the electrolysis
itself. The production of carbon anodes requires energy, so that around
18,000 kWh are needed per ton of aluminum.15 Direct CO2 emissions
for aluminum are therefore bounded by the stoichiometry of Eq. 3,
while indirect emissions are directly linked to the mode of power
generation. Aluminum shows that tonnage metal can be produced
solely relying on electricity. Production costs for this metal7,8
show that electricity accounts for 60% of the expenditure when
excluding the costs of the raw materials (carbon anode, alumina).
At 13,000 kWh/t for electrolysis, this implies an equivalent cost for
electricity at $0.05/kWh. This number matches what is often put forth
as the future costs of C-free electricity generation, highlighting the
real opportunity offered by electrochemistry.
Table I. Features of existing technologies for Fe, Cu, and Al extraction from their feedstock (concentrates).
Specific Plant Total Energy
Conversion Energy Productivity Managed
Costs ($) (kWh/t) (t/h) (Primary) (MW)
Fe 325 5000 457 2283
Cu 320 3600 46 164
Al 1100 18000 46 822
64 The Electrochemical Society Interface • Summer 2017 • www.electrochem.org
The three metals have therefore key technical challenges to
further integrate low GHG electricity and embrace the requirements
by society of a more efficient usage of energy or mined products as
well as a lower environmental impact. The three metals also have
economy of scales and exceptional productivity, which need to be
maintained in order to allow affordability. Those are briefly reviewed
below in order to define the conditions in which electrolysis, with its
(2) efficient use of energy, selectivity, unique control of productivity and
flexibility could become a viable alternative to existing routes.
Productivity, Footprint, and Scale
Table I provides some of the features of existing Fe, Cu, and Al
producing plants (smelters). These plants are nowadays integrated,
going from ore concentrate to a semi-finished product (rolled coils for
Fe, ingots for Al, and cathode plates for Cu), with different capacity
and productivity per square meter. The ranking in capacity matches
mankind’s consumption rate: 4,000,000 tpa of iron, a productivity
that is around 10 times larger than for aluminum at around 400,000
tpa, similar to that of recent copper smelters. Columns 5 and 6 show
the footprint and specific productivity of the reactors for Eq. 1–3
accounting for the unit operations where reactant preparation and
product recovery and refining are conducted. Al and Fe are entirely
reduced and refined in the liquid state, while copper undergoes
electrorefining in the solid state as an ultimate step, a notoriously low
productivity process.
Smelters cover large areas, though only a small surface is actually
dedicated to Eq. 1, 2, or 3. Most of the surface is occupied by unit
operations that handle and prepare the reactants, or separate, recover
and purify the products and by-products. Cu and Fe have a similar
productivity per square meter, twice larger than Al. The amount of
energy handled at smelters is of consequence, equivalent to very
large power plants. This feature suggests the integral role the metal
extraction sector can play in energy management in any community.
From a production cost standpoint, novel electrolytic process for
these three metals must exhibit the same conversion costs as today’s
(3) technologies (see column 2 in Table 1). Considering that 60% of
conversion costs for electrolytic extraction come from electricity,
as currently found for aluminum electrolysis, the assumption of an
electricity cost at $0.05/kWh allows one to calculate the electrical
energy budget available for Fe, Al, and Cu extraction. Current
aluminum and copper conversion costs have a respective “available”
electricity budget at 13200 and 3840 kWh/t, comparable with the
overall energy expenditure of today’s technology. The total electricity
consumption that could be afforded for Fe is around 3900 kWh/t,
which is lower than today’s energy consumption of an integrated
steel plant. Assuming the footprint for the reduction steps in smelters
may be used as a proxy for capital costs (column 6), the specific
productivity realized for an aluminum electrolysis cell today would
have to be at least doubled for iron and steelmaking. Assuming the
production capacity of the current smelters is optimized for the
capital and conversion costs as well as the market reality presented
above, the overall production rate for steel would have to be 10 times
larger than for aluminum or copper. Are those metrics reasonable
for electrochemical reactors? It is proposed hereafter to review the
situation for aluminum electrolysis production, and use this as the
baseline for extrapolating to Fe and Cu.
Footprint for
Reduction (m2) kg/h/m2 Plant Capacity and Footprint Estimates
640000 0.71 4 Mtpa, includes coke plant, sinter plant, blast furnace,
BOF, oxygen plant
64000 0.71 400 ktpa, includes flux preparation, smelter, acid plant,
oxygen plant, electrorefining
145000 0.31 400ktpa, includes anode plant,
gas treatment, electrolysis hall
 Hall-Héroult as a Baseline
As shown above, aluminum today is entirely produced by
electrolysis. The core of aluminum extraction is electrolysis
conducted in a Hall-Héroult cell where Al2O3 is dissolved at around
3 wt% in a molten fluoride bath mostly composed of cryolite
(81 wt% Na3AlF6, 11% AlF3, 5% CaF2) at 960 °C.17 The cell
adopts a horizontal design where a gravity driven separation of the
products is obtained. Consumable carbon anodes at the top evolve
CO2, and liquid aluminum is recovered at the bottom cathode. The
liquid aluminum (purity >99%) is periodically siphoned, on a yearly
average of 3.5 t/day per cell. Al2O3 is periodically fed to maintain a
concentration of a few weight percent. The key features of a modern
electrolytic cell16 are presented in the first line of Table II. A very high
cathode current density (0.8 A/cm2) and current efficiency (+95%)
justify the productivity and costs. Figure 3 shows that remarkable
electrochemical engineering efforts have been accomplished since the
discovery by Hall and Héroult [See “ECS Classics: Hall and Héroult
and the Discovery of Aluminum Electrolysis,” T. Beck, Electrochem.
Soc. Interface, 23(2) 36 (2014).]. Those progresses enabled an
increase in the cell dimensions and increase in the amount of current
flowing in a single cell. Improvements in faradaic efficiency and heat
management to decrease operational costs have also been significant.
Today energy losses amount to around 53%.17
energy consumption for a process following Eq. 4 being 9260 kWh/t
(compared to 6338 kWh/t for Eq. 3 with carbon), inert anodes
are anticipated to enable a net reduction in energy consumption
and operating costs for aluminum production (see Ref. 21 for the
underlying engineering arguments). This is not entirely surprising for
electrochemical engineers who may recall that the “decarbonization”
of chlorine production by electrolysis (deployment of dimensionally
stable anodes instead of graphite for Chlor/Alkali electrolysis) also
led to drastic cost and energy savings.28,29
Targets
The direct electrochemical decomposition of metal compounds
eliminates carbon or fuel from the chemical basis of metal extraction.
It requires developing a technology where Eq. 5 is conducted solely
with the use of low GHG-electricity:
MX → M (l ) + 1 2 X 2 ( g ) (5)
For prompt adoption, MX is ideally selected from the major
compounds of the feedstock available today from existing mining and
beneficiation operations, i.e., Fe2O3 for iron or CuFeS2 for copper.
The only by-product is O2(g) from an oxide concentrate, and S2(g)
from a sulfide concentrate. Both are very valuable in the context of
clean combustion technologies, with S2(g) having the advantage of
(continued on next page)

Direct Decomposition:
The Next Challenge?
 
Example of Inert Anode for Aluminum
As seen above, carbon anode consumption in Eq. 3 for aluminum
!
 

 

electrolysis means that even with a C-free power source, the extraction 
of aluminum as practiced today will emit CO2. Therefore the industry 






has, since the early days of Hall,19 envisioned changing the chemical
basis of aluminum production from alumina by accomplishing the 
direct decomposition Eq. 4 with a non-consumable anode: 
Al2O3 → 2 Al (l ) + 3 2 O2 ( g ) (4) 
As may be anticipated from the chemistry and electrochemistry 
of molten cryolite, the molten fluoride electrolyte being designed to 
dissolve most oxides, finding an anode material to evolve oxygen
in a Hall-Héroult cell is a remarkable challenge.20,21 It is difficult to 
find a stable conductive but passivating layer on anode materials 
for the conditions described in Table II. In addition, the reactivity
of aluminum means that most other elements present in the molten
electrolyte will be reduced preferentially, implying contamination 

of the metal product at the cathode. Nevertheless, some promising
developments have been reported using metal, ceramic, or composite
anodes, close to commercial demonstration in the early 2000s with  
publicized efforts from companies such as Alcoa or Moltech, a            
company founded by Vittorio De Nora.21 Recent updates22 from
China,23 Russia,24 the European Union,25,26 and the United States27
point to a renewed interest in this area, though not much transpired Fig. 3. Variation of the specific energy consumption (left, closed circles) and
into electrochemical engineering literature. Despite the minimal cell amperage (right, open circles) for Al electrolysis. From Ref. 15 and 18.

Table II. Key features of existing HH cells for aluminum and projection of hypothetical performances for Fe and Cu. A cathode area of 54m2 is used
(18mx3m). (min. corresponds to the minimum thermodynamic, 53% loss to the heat efficiency of HH, 33% to a cell with enhanced heat management).
Cell Voltage Faradaic Energy Consumption Cathode Current kg/h/m2 Production Rate Cell Amperage
in V Efficiency in kWh/t Density in A/cm2 (Cathode) in t/day in kA
Al today 4.26 0.95 13380 0.8 2.55 3.4 440
Fe (min.) 1.72 0.95 2600 3.9 25.50 33.0 2087
Fe (53% loss) 3.65 0.95 5532 3.9 25.50 33.0 2087
Fe (33% loss) 2.56 0.95 3881 3.9 25.50 33.0 2087
Cu (min.) 1.30 0.95 1976 0.23 5.10 6.6 122
Cu (53% loss) 2.77 0.95 4204 0.23 5.10 6.6 122
Cu (33% loss) 1.95 0.95 2949 0.23 5.10 6.6 122

The Electrochemical Society Interface • Summer 2017 • www.electrochem.org 65

Allanore
(continued from previous page) The energy consumption estimated for Cu direct decomposition,
at 4204 kWh/t using the existing performance of HH cells (53%
losses) is not yet compatible with the electricity budget available at
being condensable and transportable for remote energy generation or
$0.05/kWh derived above (3840 kWh/t). For Cu, energy management
safe storage. Developing such a technology is a challenge. Indeed,
improvements for electrolysis are required to be at par with today’s
to substitute existing technologies, the new electrolysis processes
conversion costs and losses can only represent 45% of the electricity
need to exhibit the cost, scale and productivity highlighted in Table I
consumed. If losses can be reduce to 33%, direct copper electrolysis
and discussed above. To compete on capital costs, the production per
would enable reduced energy consumption for copper extraction
unit of time and per unit of area needs to be comparable to existing
(2949 kWh/t). Matching specific surface productivity of today’s
technologies. Aluminum electrolysis technology, with its high
operations call for a current density at around 0.23 A/cm2, around 3
productivity gains (see Fig. 3), shows that producing a liquid metal
times what is found today in copper aqueous electrowinning.
enables the separation, handling and separation of the metal from
For iron, the energy losses experienced today in HH cells are
a cell without interrupting the current. For iron, an electrolysis cell
not compatible with the cost of the final product. Indeed, affordable
technology of the same dimensions as today’s HH cell would have
iron made by Eq. 5 driven by electrolysis requires a maximum of
to produce 10 times more liquid metal per hour, every hour, every
3900 kWh/t, which could not be achieved with 53% losses. A direct
day, every year, and for several years. The energy budget available
electrolytic decomposition cell for iron production would need to
is dictated by the cost of electricity, with special restrictions to the
achieve less than 33% energy loss, a challenge that requires careful
various contributions of the cell voltage introduced in Ref. 13 and
mastering of heat transfer at 1538 °C. Existing electrical processes
detailed in Ref. 28. Hereafter, a projection of the electrochemical
at such high temperatures suggest that such performance is possible,
engineering metrics necessary for Fe and Cu direct electrolysis
though yet to be proven for electrolysis.30 In terms of productivity,
to compete with existing technology is proposed, using today’s
matching existing performances for iron requires a current density
aluminum electrolysis performances as a baseline.
of around 4 A/cm2, a figure pointing to a need for a breakthrough
in electrochemical reactivity of metal ions. For Cu, Fe, and Al,
Engineering of an Electrolysis Cell the requirement for high productivity highlights the relevance of
Producing a Liquid Metal Commodity producing a liquid metal product, avoiding the limitations inherent to
Assuming the production of a liquid metal, the existing HH cell electro-crystallization. The current example of Hall-Héroult cells or
dimensions and efficiency can be used as a baseline to evaluate the past amalgam Cl2/Na production with a liquid cathode at a current
the features of a similar process to make Fe (Tm = 1538 °C) and density up to 1.5 A/cm2 are strong indicators of the benefits of such
Cu (Tm = 1085 °C). For a mitigation of environmental impact, the an approach. 28
gaseous anodic product evolves on a non-consumable anode (O2 for
Fe, S2 for Cu), meaning a significant departure and improvement of Consequences on Electrolyte
the anode design for gas evolution and removal (see Ref. 21).
The aluminum cells today are self-heating reactors, where the
and Electrochemical Engineering
Some of the figures calculated above are challenging for electrical
engineering of irreversibility (Joule effect due to the ohmic drop)
and mechanical engineering. For example, as suggested in Table
is used to maintain the temperature of the electrolysis cell. The
II, line 4, how to safely operate a 2000 kA cell at around 1600 °C
cell operates at 960 °C, with energy losses of around 53%. Some
for liquid steel production, with the corresponding recovery of
of those heat losses are purposely engineered to allow the formation
120 Nm3/ min of O2, all at a terminal voltage of less than 2.6 V?
of a frozen side-wall to contain molten cryolite. Additional losses
Electrochemists are also challenged to find conditions that could
include heat transfer through the bottom, walls, top electrodes and
actually enable Eq. 5 to be driven at such a rate, with a selectivity
gas leaving the cell.15 The current efficiency for aluminum is very
greater than 95%. Considering the desire to produce liquid metal,
high, greater than 95%, an important feature for affordable tonnage
high temperature molten electrolytes are needed. Table II shows
metals production.
the conditions of the HH process, which again can be used as an
Knowledge of the energy and current efficiency allows one to
inspiration. Considering the cathode current density used in today’s
evaluate the actual energy consumption anticipated to conduct Eq. 5
HH cells corresponds to 70% of the limiting current density—it is
for Fe and Cu. Maintaining the existing productivity and footprint for
common in electrodeposition not to run at the limiting current to
those metals (see Table II for existing data) calls for a re-evaluation of
avoid uneven growth of the metal—it is possible to evaluate the
the total current flowing in electrolysis cells, meaning operating at a
equivalent mass transfer conditions existing at the cathode via:
different current density. The current and current density recalculated
for Cu and Fe are shown in Table II (column 5), where a single jlim 1
kD = (6)
HH cell is considered with a cathode area of 54 m2.14 For iron, the 3F [ M 3+ ]
production rate has been multiplied by 10 to match today’s smelter
capacity differences with Al. For copper, the productivity by square Using a bulk concentration of Al3+ equivalent to 10 mol/L,1 the
meter has been scaled by 1.13, to match the difference in smelter equivalent mass transfer coefficient amounts to around 4.10−6 m/s,
footprint. familiar to aqueous and molten salts electrochemists. Assuming

Table III. Important physical chemical data for some molten electrolytes (μ: viscosity in mPa.s; ρ: density in g.cm−3; κ: conductivity in S.cm−1).
Pros Cons
Halides (Ref. 36, 37, and 38) high κ [0.02 – 6] - temperature limited to <1200 °C
low μ [1 – 6] - low solubility for O2−, S2−
low ρ [1.3 to 1.9] - possible liquid metal solubility
Fluorides (Ref. 36) high κ [0.1 – 10] - temperature limited to <1200 °C
low μ [1 – 20] - corrosive
low ρ [1.8 to 4] - vapor pressure
Oxides (Ref. 31 and refs therein) high solubility for oxide - high viscosity in presence of network former
low vapor pressure - electronic conduction
Sulfides (Ref. 39) high solubility for sulfides
- vapor pressure
high κ
- electronic conduction
low µ

66 The Electrochemical Society Interface • Summer 2017 • www.electrochem.org

an electrolyte with similar mass transfer coefficient as for HH, one
can calculate the equivalent bulk concentration of Cu or Fe cations
required to achieve the current densities evaluated in Table II. The
calculation suggests that electrolytes with at least 5 mol/L and
50 mol/L of respectively Cu+ and Fe3+ cations needs to be dissolved
from the feedstock.
Which molten electrolyte could exhibit such features? Table
III lists some of the possible candidates, where molten oxides (see
Ref. 31 for a review), and molten sulfides have recently received
renewed attention. Molten halides are well known electrolytes with a
limited solubility for oxides and sulfides, and a rather limited range
of temperature. Liquid copper production has been demonstrated
in such halides,32 but challenges inherent to the anode reactions
remain. Molten fluorides are also well recognized candidates and
have the reported challenges of being very corrosive to oxides, again
exhibiting a fairly limited range of temperature stability. Molten
sulfides remain understudied, and recent efforts toward high-melting
point quasi-binary and -ternary systems indicate a possible path
forward to the direct decomposition of sulfides to metal and sulfur.33
In this situation, the handling and selectivity of direct electrolysis for
multiple metal species coming from the sulfide concentrates remain
to be demonstrated, e.g., Fe but also Se, As, or Ag from chalcopyrite.
It indeed remains to be demonstrated that Eq. 5 can be conducted
from ore concentrates available on the market. Molten oxides are
best suited to treat oxide ores, and exhibit a wide range of operating
temperature.
The general lack of understanding and study of the physical
chemistry, thermodynamic and electrochemical properties of all those
electrolytes is the first challenge faced by electrochemical engineers,
and a concerted effort from materials scientists, chemists and
electrochemists would greatly enhance the rate of progress in the use
of those electrolytes. The high solubility of metal cations is necessary
for competitive productivity, and molten oxides and sulfides are
interesting candidates from such a standpoint. Equally important is
the concentration of the electronegative species that forms the metal
feedstock compound, i.e., the species oxidized at the anode to yield
X2(g) in Eq. 5. This is particularly important for electrolytes that are
based on different electronegative elements than in the feedstock,
e.g., oxides in molten fluorides or sulfides in molten halides. As
known in HH cells as the anode effect, a low concentration of oxygen
next to the anode may lead to the oxidation of another species, such
as CFC in fluoride-based electrolytes.33 The author has in particular
studied such mass transfer issues in molten oxides, in the context of
oxygen ions oxidation to oxygen gas,34,35 showing that natural and
bubble-induced convection are likely essential phenomena to support
the range of anode current densities necessary for commodity metal
extraction by electrolysis.
Summary
Iron, aluminum, and copper have a cost per unit and production
capacity that ranks them as commodity. The success of aluminum
production by electrolysis enabled this metal to become such a
commodity, and the perspective of cost effective C-free electricity
offers a unique opportunity to envision new electrolytic processes
for Cu and Fe. Those processes will have to exhibit stringent
productivity, high-energy efficiency, and evolve environmentally
compatible products at the anode to maintain the sustainability of
both metals. From a productivity standpoint, the production of liquid
metal is an important feature that calls for the development of high
temperature electrolytes compatible with the metal feedstocks. This
challenge requires a multidisciplinary endeavor, where the physico-
chemical understanding of high temperature electrolytes and the
electrochemistry of both cathodic and anodic reactions will need
to be provided to enable the design of competitive electrochemical
reactors with unique performance. Hall-Héroult Cells,” W.S. Peterson and R.E. Miller, Editors, p.
© The Electrochemical Society. DOI: 10.1149/2.F05172if.
a
This concentration is chosen as an order of magnitude. The actual species
reduced at the cathode are not Al3+ cations and the mechanism actually
involves fluorinated species of Al.
The Electrochemical Society Interface • Summer 2017 • www.electrochem.org 67
About the Author
Antoine Allanore’s research applies to
sustainable materials extraction and
manufacturing processes, in particular using
electrochemistry. Allanore joined MIT in 2010
where he devised a new inert anode material for
oxygen evolution at 1600 °C in molten oxide for
steel production. As a faculty in the Department
of Materials Science & Engineering, he has
developed numerous alternative approaches for
metals and minerals extraction and processing.
With an emphasis on electrochemical methods for both analytical and
processing purposes, his group combines experimental and modeling
approaches to promptly investigate the ultimate state of condensed
matter, the molten state. Allanore is a member of The Electrochemical
Society since 2006. He was awarded The Minerals, Metals &
Materials Society (TMS) DeNora Prize in 2012, recognizing
outstanding contribution to the reduction of environmental impacts,
especially focused on extractive processing, as well as the Early
Career Faculty award also from TMS. He may be reached at
allanore@mit.edu.
http://orcid.org/ 0000-0002-2594-0264
References
1. Worldsteel Statistics, https://www.worldsteel.org/steel-by-topic/
statistics.html
2. Word-Aluminum, http://www.world-aluminum.org
3. International Copper Study Group, http://www.icsg.org
4. International Lead and Zinc Study Group, http://www.ilzsg.org/
static/home.aspx
5. S. H. Ali, D. Giurco, N. Arndt, E. Nickless, G. Brown,
A. Demetriades, R. Durrheim, M. Amélia Enriquez, J. Kinnaird,
A. Littleboy, L. D. Meinert, R. Oberhänsli, J. Salem, R. Schodde,
G. Schneider, O. Vidal, and N. Yakovleva, Nature, 543, 367
(2017).
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