J. Electrochem. Sci. Technol., 2018, 9(4), 320-329
− 320 −
Li- and Na-ion Storage Performance of Natural Graphite via
Simple Flotation Process
Noureddine Ait Laziz1, John Abou-Rjeily2, Ali Darwiche3, Joumana Toufaily4, Abdelkader Outzourhit1,
Fouad Ghamouss2, and Moulay Tahar Sougrati3*
1Laboratoire de Nanomatériaux pour l'énergie et l'environnement (LN2E)- Université Cadi Ayyad, Marrakech
2Faculté des Sciences, Laboratoire de Physico-Chimie des Matériaux et des Electrolytes pour l’Energie (PCM2E),
Université François Rabelais, France
3Institut Charles Gerhardt, CNRS UMR 5253, Université de Montpellier, 34095 Montpellier Cedex 5, France
4Laboratory of Applied Studies for Sustainable Development and Renewable Energy (LEADDER); MCEMA, Lebanese University
Abstract : Natural graphite is obtained from an abandoned open-cast mine and purified by a simple, eco-friendly and
affordable beneficiation process including ball milling and flotation process. Both raw graphite (55 wt %) and its con-
centrate (85 wt %) were electrochemically tested in order to evaluate these materials as anode materials for Li-ion and Na-
ion batteries. It was found that both raw and purified graphites exhibit good electrochemical activities with respect to lithium
and sodium ions through completely different reaction mechanisms. The encouraging results demonstrated in this work suggest
that both raw and graphite concentrates after flotation could be used respectively for stationary and embedded applications.
This strategy would help in developing local electrical storage systems with a significantly low environmental footprint.
Keywords : Natural graphite, Na-ion batteries, Li-ion batteries, Energy storage, Stationary application, Froth flotation
Received : 20 July 2018, Accepted : 7 August 2018
1. Introduction
While some regions of the world are preoccupied
with growing energy consumption, CO2 emissions,
and climate change, others are still suffering from the
lack of conventional energy, particularly electricity,
which penalizes their socio-economic development.
This is particularly the case of around 18% of the
world’s population, living mostly in rural areas of
South Asia and Sub-Saharan Africa [1]. Grid exten-
sion to such areas is not usually economically feasi-
ble. However, most of these regions are endowed
with huge renewable energy (solar and/or wind) [2]
as well as minerals resources. Consequently, invest-
ing in the harvesting and control of these energies
would undoubtedly reduce the energy inequality and
promote economic activities necessary for the
improvement of the living conditions of a significant
portion of populations living in these areas. The inter-
mittence of renewables energies sources, which is
one of the hurdles for their reliability and dispatch-
ability, can be circumvented by the development of
efficient and cost-effective energy conversion and
storage systems. Electrochemical storage, a solution
that has proven itself for embedded systems, may be
adopted in this case provided that affordable materi-
als not requiring expensive and extensive processing
could be used.
Recently, our team (LN2E), evaluated the perfor-
mance of a standalone solar photovoltaic power plant
supplying electricity to the rural village Elkaria in the
province of Essaouira - Morocco [3], where energy
storage was provided by 24 lead-acid batteries. The
choice of this technology for such small systems
(some kWh) in isolated rural site is justified by the
best compromise between performance and cost that
it offers.
*E-mail address: Moulay-tahar.sougrati@umontpellier.fr
DOI: https://doi.org/10.5229/JECST.2018.9.4.320
Research Article
Journal of Electrochemical Science and Technology
Noureddine Ait Laziz et al. / J. Electrochem. Sci. Technol., 2018, 9(4), 320-329 321
Li-ion batteries are also among the candidate tech-
nologies for storage of clean electricity for such
applications. However, despite their high reversibility
and efficiency, they are still relatively expensive due
to the materials and processes used in their fabrica-
tion. It is therefore very important to make this tech-
nology affordable to low-income populations by
focusing on cost effective and naturally occurring
materials that require only minimal physicochemical
treatments.
Graphitic carbon is the most commonly used anode
material in today’s commercial lithium-ion batteries
[4,5]. In fact, various forms of both synthetic and nat-
ural graphite have proven to be excellent lithium
intercalation compounds [4,6]. Graphite has a theo-
retical specific capacity of 372 mAh/g [7], and
depending on its type it can sustain a practical spe-
cific capacity more than 360 mAh/g [8]; which is
close to theoretical limit. It also exhibits a low flat
potential profile versus lithium and a good charge-
discharge cycle stability which is considered to be
one of the most important criteria for reliable and
long-lived lithium-ion batteries [9,10].
On the other hand, despite its great success for Li-
ion batteries, graphite exhibits a lower specific capac-
ity when used as a Na-ion battery anode, because of
its inability to form stable compounds with sodium
[11,12]. However, Jache et al. discovered a new
approach were graphite is capable of Na insertion and
extraction via co-intercalation process with diglyme-
based (diethylene glycol dimethyl ether) electrolytes
[13]. This mechanism results in stage 1 ternary com-
pound exhibiting excellent reversibility and superior
cycle-life with a capacity close to 100 mAh/g. Subse-
quently, Kim et al reported a Na+-solvent co-interca-
lation behavior in natural graphite using ether-based
electrolyte [14].
The characteristics of synthetic graphite can be tai-
lored in the manufacturing process making it the best
choice for mobile applications. However, its cost is
prohibitive for large-scale use such as in stationary
storage infrastructures. As a consequence, natural
graphite has emerged as an attractive alternative
because of its low cost and its wide availability
across the world. However, natural graphite requires
beneficiation for obtaining desired grade for various
end-uses. Various techniques can be applied to
improve graphite grade including physical, chemical
and thermal methods [15]. However, Because of nat-
ural hydrophobicity of graphite, flotation is the most
used technique for its beneficiation [15]. In fact, a
survey of literature indicates that graphite was the
first mineral to be concentrated by flotation by Bessel
Brothers in 1877 [15]. Thereafter, considerable
advances in flotation were performed making it the
economically competitive process to enrich mineral
even low grade ore considered as waste [16]. It is
thus not surprising that billions of tons of ore are ben-
eficiated trough this technique annually. Further-
more, about 95% of the base metal produced are
treated by flotation process [16]. Surprisingly, only a
few studies focused on the purification and electro-
chemical performance of natural graphite in its raw
and purified forms in the field of secondary batteries
especially without the need of applying costly and
time consuming purification methods. Most recently
natural graphite was cycled vs. Li before using them
as a source of graphene with a reversible capacity
less than 200 mAh/g. The aim of this work is to study
the possibility of making an electrochemical storage
system from abundant and inexpensive minerals in
Morocco. To this end, the electrochemical perfor-
mances of naturally abundant graphite from an open-
cast Moroccan mine as an anode material for Li-ion
and Na-ion batteries were evaluated. This material is
studied in its raw state and after a purification process
using clean and low-cost process combining ball
milling and flotation separation. To our knowledge,
Moroccan natural graphite has never been studied in
the field of secondary batteries. This abundant natural
resource could potentially participate in a suitable
development of the local economy. Moreover, Li/Na-
ion technologies based on cheap materials are in line
with the Moroccan strategy aiming at developing sta-
tionary storage systems for locally produced the
green energy [24]. It is also important to note that this
approach can contribute to reduce the negative
impact on environment of the pollution due to aban-
doned mining sites as evidenced in recent studies
[25,26].
2. Experimental
Samples of Moroccan natural graphite were
obtained from the abandoned Sidi Bou Othmane
open-cast mine located 33 kilometers north of Mar-
rakesh city (Morocco). This region was also oper-
ated for Pb, Zn, and pyrite extraction until 1980 [27].
