A dual–ion battery using diamino–rubicene as anion–inserting positive electrode material

Article abstract of DOI:10.1016/j.elecom.2016.09.002

A novel and non-polymeric anion-inserting electrode material has been designed and prepared for promoting research on molecular ion rechargeable batteries: 5,12-diaminorubicene (DARb). The apolar core structure of a rubicene molecule has been coupled to two amino-groups for producing an original conjugated primary diamine exhibiting low affinity for polar solvents such as common carbonate-based battery electrolytes. The electrochemical reactivity of this organic molecule has been probed in a dual-ion cell configuration (vs. Li) using six different electrolyte formulations in terms of solvent (PC, EC-DMC) and lithium salt (LiPF₆, LiClO₄, LiTFSI). This diamino-rubicene material systematically showed a reversible electroactivity and promising performances when using 1?M LiPF₆ in EC:DMC (1:1?vol.%) as the electrolyte, such as an average potential of ~?3.4?V vs. Li⁺/Li⁰, an initial capacity of 115?mAh·g^??1 and a good capacity retention over 60?cycles without any optimization.

Full text of DOI:10.1016/j.elecom.2016.09.002

Electrochemistry Communications 72 (2016) 64–68
Contents lists available at ScienceDirect
Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom
A dual–ion battery using diamino–rubicene as anion–inserting positive
electrode material
Élise Deunf a, Pablo Jiménez a, Dominique Guyomard a, Franck Dolhem b,c, Philippe Poizot a,d,
⁎
a
Institut des Matériaux Jean Rouxel (IMN), UMR CNRS 6502, Université de Nantes, 2 rue de la Houssinière, B.P. 32229, 44322 Nantes Cedex 3, France
b
Laboratoire de Glycochimie, des Antimicrobiens et des Agroressources (LG2A), UMR CNRS 7378, Université de Picardie Jules Verne, 33 rue Saint-Leu, 80039 Amiens Cedex, France
Réseau sur le Stockage Électrochimique de l'Énergie (RS2E), FR CNRS 3459, France
c
d
Institut Universitaire de France (IUF), 103 bd Saint-Michel, 75005 Paris Cedex 5, France
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 4 August 2016
Received in revised form 1 September 2016
Accepted 2 September 2016
Available online 06 September 2016
A novel and non-polymeric anion-inserting electrode material has been designed and prepared for promoting re-
search on molecular ion rechargeable batteries: 5,12-diaminorubicene (DARb). The apolar core structure of a
rubicene molecule has been coupled to two amino-groups for producing an original conjugated primary diamine
exhibiting low affinity for polar solvents such as common carbonate-based battery electrolytes. The electrochem-
ical reactivity of this organic molecule has been probed in a dual-ion cell configuration (vs. Li) using six different
electrolyte formulations in terms of solvent (PC, EC-DMC) and lithium salt (LiPF6, LiClO4, LiTFSI). This diamino-
rubicene material systematically showed a reversible electroactivity and promising performances when using
1 M LiPF6 in EC:DMC (1:1 vol.%) as the electrolyte, such as an average potential of ~3.4 V vs. Li+/Li0, an initial ca-
pacity of 115 mAh·g−1 and a good capacity retention over 60 cycles without any optimization.
© 2016 Elsevier B.V. All rights reserved.
Keywords:
Organic batteries
Anion insertion
Diamino-rubicene
Redox-active amine
Dual-ion cell
1. Introduction
the field attracting much interest from the energy storage community
as highlighted in several recent reviews on the topic [10–12]. In partic-
Owing to the depletion of fossil fuels and the impacts of the subse-
quent global warming, the concept of sustainability is rapidly expanding
to our technology-oriented society. While clean energy conversion and
storage systems are being aggressively pursued, current rechargeable
systems such as secondary (rechargeable) batteries are facing possible
environmental concerns due to the large-scale production, the use of
non-renewable resources (ores) and high-temperature synthesis routes
in elaborating active electrode materials [1–4]. Consequently, we can
easily perceive the interest in promoting new generations of low-pollut-
ing electrochemical storage devices. One possible alternative could be
nestled in the development of redox-active organic compounds because
the latter are based on more abundant chemical elements and possess
some versatile electrochemical properties. For instance, beyond the
redox potential tuning by designing the structure arrangement (see
for example Refs. 5–7), organics can interestingly operate according to
two types of electrochemical mechanisms (both n- and p-type1) and
in various cell configurations, as reported by Novák et al. many years
ago [9]. Over the last ten years, significant progress was achieved in
ular, long-term cycling stability curves (N1000 cycles) have been re-
ported by Zhou's group and Yao's group [13–15] for Li-organic
batteries using carbonyl-based polymers as the positive electrode. How-
ever, elaborated in their charged state, such n-type organic electrode
materials reversibly accommodate lithium at a relatively low operating
potential (b2.4 V vs. Li+/Li0). Alternatively, p-type redox-active organic
compounds which involve an anion-inserting process upon charging
may react at higher potentials [8,9] bringing to us another playground
in designing organic electrochemical storage systems including the de-
velopment, in principle, of molecular ion batteries [9] as recalled by Yao
and co-workers in a visionary study [16]. Although existing p-type elec-
trode materials consist in organic polymers and oligomers (see for in-
stance, refs 9, 17–23), we have recently reported that crystallized host
organic structures based on aromatic secondary amines can electro-
chemically accommodate anions at potentials higher than 3.2 V vs.
Li+/Li0 [24,25].
In light of its stunning electrochemical and chemical properties, we
decided to dig further on the potentiality of low-weight aromatic
amines as intercalation electrode material. We are proposing in this
study a novel organic electrode molecule belonging this time to the pri-
mary amine family and built on a condensed aromatic rubicene system.
Also known as a molecular fragment of C70, this organic backbone is a
stiff polycyclic aromatic hydrocarbon with planar π-orbital surfaces po-
tentially providing good intermolecular electronic coupling [26,27]. Al-
though poorly investigated in the literature, rubicene possesses a large
⁎
Corresponding author at: Institut des Matériaux Jean Rouxel (IMN), UMR CNRS 6502,
Université de Nantes, 2 rue de la Houssinière, B.P. 32229, 44322 Nantes Cedex 3, France.
E-mail address: philippe.poizot@cnrs-imn.fr (P. Poizot).
n-type structures involve upon oxidation an ionic compensation with cation release
1
whereas p-type structures imply an anion uptake. Note that p- and n-type structures are
also named System A and B, respectively, according to Hünig's classification [8].
http://dx.doi.org/10.1016/j.elecom.2016.09.002
1388-2481/© 2016 Elsevier B.V. All rights reserved.

É. Deunf et al. / Electrochemistry Communications 72 (2016) 64–68
65
apolar moiety that may intrinsically limit its affinity and tendency to be
solvated by polar solvents such as common carbonate-based battery
electrolytes. In addition, the extended aromatic core of rubicene is suit-
able to stabilize positive charges and unpaired electrons by delocaliza-
tion, thus favoring the reversibility of p-type redox reactions by
avoiding side reactions. We therefore coupled the rubicene core with
the redox properties of amino groups to design a diamino-rubicene (de-
noted DARb) as a first prototype of non-polymeric active electrode ma-
terial based on a conjugated primary diamine. In this communication,
we report the preparation of the DARb compound and its preliminary
anion-inserting properties measured in a lithium half cell.
DMSO): δ 148.5, 140.2, 137.9, 131.7 (2C), 128.3, 127.6, 124.7, 124.2,
123.5, 119.9, 113.3, 108.1; ESI-HRMS m/z 357.1386 [M + H]+ (calcd.
for C26H17N2, 357.1392).
2.4. Electrochemical study
The electrochemical performance of the material were tested vs.
lithium in a Swagelok®-type cell using a Li metal disc as negative elec-
trode and two fiberglass separators soaked with the desired electrolyte
(six different formulations). The positive electrodes were prepared
without binder in an argon-filled glove box by hand-milling powder
of DARb with 33 wt.% of carbon black (Ketjenblack EC-600JD,
AkzoNobel) with a typical loading of 4 mgcm2 mg·cm−2 of active mate-
rial. The cells were cycled in galvanostatic mode using a MPG-2 system
(Bio-Logic S.A., Claix, France).
2. Material and methods
2.1. Chemicals
Fluorenone (98%, Alfa Aesar), magnesium turnings (99.8%, Alfa
Aesar), sodium sulfide hydrate (N60%, Aldrich), acetic acid (N99%, Al-
drich), nitric acid (69.5%, Carlo Erba) and toluene (Carlo Erba) were
used as received. Supporting salts such as LiClO4 (Aldrich, battery
grade), LiPF6 (Novolyte) and LiTFSI (Novolyte) were also used without
further purification. Propylene carbonate (PC), ethylene carbonate
(EC) and dimethyl carbonate (DMC) were of battery grade and pur-
chased from Novolyte.
3. Results and discussion
The electrochemical behavior of aromatic amines has been widely
investigated in liquid media [29–31] and one common application in
molecular electrochemistry comes from the preparation of conducting
polymers by electro-oxidation [32–34]. The oxidation reaction proceeds
through the reversible formation of a radical cation, which is stabilized
by electron delocalization on the aromatic-core structure giving usually
rise to reversible faradaic peaks in cyclic voltammetry [29–31]. In solid
state electrochemistry, the redox activity of amino groups involves a
concomitant anion insertion process for maintaining charge neutrality
within the electrode material. On the basis of the available literature
till date, it seems however that the broad family of redox-active conju-
gated amines has been poorly investigated in battery applications ex-
cept the particular case of polyaniline [9,35,36].
2.2. Analytical techniques
Infrared spectra were recorded on a FT-IR Bruker Vertex 70.
Electrospray ionization high-resolution mass spectrometry (ESI-
HRMS) data were obtained in the negative ion mode with a Q-TOF Ulti-
ma Global instrument (Waters-Micromass) equipped with a pneumat-
ically assisted electrospray ion source (Z-spray) and an additional
sprayer for the reference compound (LockSpray). 1H and 13C NMR spec-
tra were recorded on a Bruker AVANCE III 400 MHz. Chemical shifts (δ)
are given in ppm relative to TMS.
In principle, the electrochemical activity of the DARb material is ex-
pected to proceed through an initial radical cation formation (with si-
multaneous counter-ion uptake from the electrolyte) followed by a
second oxidation step leading to the dication species with fully
delocalized π-system (Scheme 1). The overall two-electron process
gives an expected theoretical capacity of 150 mAh·g−1. Since the elec-
trochemical reactivity of such an amino-compound should proceed
through a reversible anion uptake process, we aimed at evaluating sev-
2.3. Synthetic procedure
The synthesis of 5,12-diaminorubicene was inspired from a protocol
published by Sachweh and Langhals [28]. Fluorenone (20.8 mmol,
3.75 g) is melted in a flask at 100 °C under argon then magnesium turn-
ings are added (51.4 mmoles, 1.25 g). The reaction mixture is heated up
to 300 °C. Once the exothermic reaction started boiling and the mixture
turned dark red, the heating was switched off. The mixture is slowly
cooled down and the product is purified overnight via simultaneous ex-
traction–purification with boiling toluene in a homemade Soxhlet ex-
tractor. The solid product (rubicene) is recovered by filtration as a
bright red powder. The 1.96 g (6 mmol, 56% yield) of recovered crude
rubicene are then dispersed in 20 ml of acetic acid, to which 1.6 ml of
concentrated nitric acid is added dropwise. After addition, the reaction
is kept at 80 °C during 2 h. The reaction mixture is filtered and washed
with water and ethanol, and the precipitate subsequently extracted
twice with boiling toluene. The filtrated precipitate is a highly insoluble
dark purple powder (5,12-dinitrorubicene). 0.75 g (1.8 mmol, 30%
yield) of 5,12-dinitrorubicene and 23 g of hydrated sodium sulfide are
dispersed in a mixture of 16 ml of water and 130 ml of ethanol. The re-
action mixture is kept under reflux during 6 h and filtered while hot.
The precipitate is washed thoroughly with ethanol and water. After re-
crystallization from a DMF:THF mixture and drying at 90 °C under vac-
uum 0.46 g (1.29 mmol, 71% yield; 12% total yield from starting
fluorenone) of a dark blue powder are obtained, corresponding to
pure 5,12-diaminorubicene (DARb): IR (KBr pellet) ῡmax 3390, 3050–
eral guest anions characterized by different size and geometry: PF6−
,
ClO−4 and TFSI− (Li+ being the common counterion). Our recent studies
on the interest of crystallized secondary amines have also pointed out
that the anion-inserting process can be sensitive to the solvent nature
as well [24,25]. Therefore we managed to explore different electrolyte
solvents such as pure PC and the common EC:DMC (1:1 vol.%) mixture.
The active material response was thus tested with a set of six electro-
lytes made of 1 M ionic salt solutions.
In a typical electrochemical procedure, the DARb electrode material
was galvanostatically charged then discharged in a dual-ion cell config-
uration [9,37] at a cycling rate of 1 electron exchanged per diamino-
rubicene unit in 5 h (Fig. 1). Interestingly, a reversible electrochemical
activity can systematically be noted whereas common features can be
observed such as the same stepwise process, an average potential locat-
ed at ~3.4 V vs. Li+/Li0 or an initial charge capacity assigned to the up-
take of 1.5–1.7 electrons per diamino-rubicene unit. These features do
not seem influenced neither by the solvent nor the counterion nature.
However, differences arise upon cycling and notably poor electrochem-
ical stabilities for TFSI-based electrolytes. Such capacity fading could be
interpreted by an extensive rearrangement (including Coulomb repul-
sions) that undergoes the p-type active molecule while incorporating
the bulky TFSI− anions giving rise to the exfoliation of the active mate-
rial [20,24].
2830, 1610, 1480, 1380, 1230, 820, 735, 660 cm−1
;
1H NMR
In addition, some preliminary FTIR data seem indicate that this pri-
mary diamine chemically inserts solvent molecules of the electrolyte
as previously observed with secondary diamines [24,25], which could
explain the discrepancies observed in the cycling curves when using
(400 MHz, d6-DMSO): δ 8.56 (d, 2H, J = 8.8 Hz), 8.07 (d, 2H, J =
8.4 Hz), 8.02 (d, 2H, J = 6.4 Hz), 7.74 (t, 2H, J = 8.0 Hz), 7.31 (s, 2H),
6.68 (d, 2H, J = 7.6 Hz), 5.50 (s, 4H, NH2); 13C NMR (100 MHz, d6-

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É. Deunf et al. / Electrochemistry Communications 72 (2016) 64–68
Scheme 1. Proposed electrochemical process for the DARb electrode material with concomitant double anion uptake/release.
the same supporting salt. Better performances were obtained with both
LiPF6 and LiClO4 based-electrolytes regardless of the solvent composi-
tion, which can be related to closer values of the respective van der
Waals anionic volume. At this stage, the best electrochemical behavior
for the DARb electrode material in terms of reversibility and recovered
capacity is obtained when using 1 M LiPF6 in EC:DMC (1:1 vol.%), a com-
mon electrolyte formulation for Li-batteries (light blue trace in Fig. 1).
Further cycling performances regarding this cell are reported in Fig. 2.
The potential vs. specific capacity trace (Fig. 2a) shows an initial ca-
pacity of 115 mAh·g−1 (i.e., N75% of the theoretical capacity based on a
two-electron process) and above all a quite stable electrochemical pro-
file upon cycling. The stepwise process can be more accurately visual-
ized on the differential capacity curve shown in Fig. 2b. Note that the
first charging curve exhibits an electrochemical feature slightly different
compared to the subsequent cycles in the narrow 3.3 to 3.5 V potential
range. The three initial electrochemical steps become reduced to two
main peaks whereas a larger capacity value is then observed for the
step located at ~ 3.5 V on the second charge. At this stage, since the
charging process involves an anion-inserting process with bulky anions,
it is believed that the subsequent deinsertion process can induce an ir-
reversible structural change giving rise to a different electrochemical
behavior in the subsequent cycles. Although no optimization of the
composite electrode has been carried out at this time, this molecular
and non-polymeric conjugated primary diamine exhibits good capacity
retention over cycling (75 mAh·g−1 after 60 cycles) demonstrating the
potentiality offered by this p-type and apolar organic host structure.
In comparison, dilithium 2,5-(dianilino)terephthalate (denoted as
Li2DAnT) showed a rapid capacity fading when cycling at the full elec-
trode capacity range (i.e., 1 electron per amino group) under similar
electrochemical testing procedures [24].
Fig. 1. Potential vs. number of electrons exchanged per diamino-rubicene unit measured in Li half cells using DARb as the active electrode material mixed with 33 wt.% of carbon black and
galvanostatically charged then discharged at a rate of 1 electron exchanged in 5 h for six different electrolyte formulations: 1 M LiClO4/PC (red); 1 M LiPF6/PC (orange); 1 M LiTFSI/PC
(green); 1 M LiClO4/EC-DMC (purple); 1 M LiPF6/EC-DMC (blue); 1 M LiTFSI/EC-DMC (pink) (*corresponds to the anionic van der Waals volume [38]). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

É. Deunf et al. / Electrochemistry Communications 72 (2016) 64–68
67
Fig. 2. Electrochemical performance of a Li half cell composed of a mixture of DARb compound and carbon black (33 wt.%) as the positive electrode, galvanostatically cycled in 1 M LiPF6 in
EC-DMC at a rate of 1 electron exchanged per diamino-rubicene unit in 5 h. (a) Potential vs. specific capacity curve for the first five cycles; (b) Corresponding differential capacity trace for
the two first cycles; (c) Capacity retention curve together with the coulombic efficiency.
[2] J. Dewulf, G. Van der Vorst, K. Denturck, H. Van Langenhove, W. Ghyoot, J. Tytgat, K.
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A molecular electrode material presenting an exotic and apolar core
structure based on a rubicene backbone has been prepared and electro-
chemically assessed in a dual-ion cell configuration. Its redox activity is
centered on two amino groups which turned the rubicene molecule into
a p-type active material with reversible anion uptake/release, which is
able to exchange up to two electrons per molecule at high potential.
The electrochemical properties of the material were preliminary evalu-
ated towards lithium with a set of different electrolyte formulations (PC
or EC-DMC mixed with LiPF6, LiClO4 or LiTFSI). Logically, the best inser-
tion performances were obtained for smaller guest anions while the use
of 1 M LiPF6 in EC/DMC as the electrolyte led to promising cycling
curves. In principle, better capacity retention curves are expected by
using graphene as carbon additives since the rubicene planar core
should interact by physisorption on graphene forming a carbon-sup-
ported organic electrode [39,40]. This study confirms the proper elec-
trochemical activity of conjugated amines at the solid state and their
potentiality to stimulate further research in the field of molecular ion re-
chargeable organic batteries.
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