Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties

Article abstract of DOI:10.1002/anie.201600098

We report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on ⁵⁷Fe M?ssbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe-NCN into Li/Na-NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not require heavy treatments (such as nanoscale tailoring, sophisticated textures, or coating) to obtain long cycle life with current density as high as 9A g^-1 for hundreds of charge-discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides M_x(NCN)_y with M=Mn, Cr, Zn can cycle successfully versus lithium and sodium. Their electrochemical activity and performance open the way to the design of a novel family of anode materials.

Full text of DOI:10.1002/anie.201600098

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201600098
German Edition: DOI: 10.1002/ange.201600098
Batteries
Transition-Metal Carbodiimides as Molecular Negative Electrode
Materials for Lithium- and Sodium-Ion Batteries with Excellent
Cycling Properties
Moulay T. Sougrati, Ali Darwiche, Xiaohiu Liu, Abdelfattah Mahmoud, Raphael P. Hermann,
Samuel Jouen, Laure Monconduit, Richard Dronskowski,* and Lorenzo Stievano*
Abstract: We report evidence for the electrochemical activity
of transition-metal carbodiimides versus lithium and sodium.
In particular, iron carbodiimide, FeNCN, can be efficiently
used as negative electrode material for alkali-metal-ion bat-
teries, similar to its oxide analogue FeO. Based on Fe
Mçssbauer and infrared spectroscopy (IR) data, the electro-
chemical reaction mechanism can be explained by the rever-
sible transformation of the FeÀNCN into Li/NaÀNCN bonds
aggressive pace, with lithium-ion technology leading the race.
The emergence of new battery materials is linked to the
worldꢀs increasing appetite for energy storage devices for
communication, transportation, and defence systems. Ana-
lysts expect a growth in the market of primary-component
battery materials from $7.3 to $19.3 billion between 2014 and
2023. In this context, the design of new negative electrode
materials made of affordable and abundant elements, with
improved electrochemical performances compared to tradi-
tional graphite anodes, is crucial.
Among others, materials undergoing a so-called “con-
version reaction” (metathesis) form one of the largest families
of negative electrodes with interesting specific and volumetric
capacities. They include transition-metal oxides as well as
metal phosphides, sulfides, nitrides, and alloys (based on Si,
Ge, Sn, Sb), all following the “conversion reaction”
57
[
1]
during discharge and charge. These new electrode materials
exhibit higher capacity compared to well-established negative
electrode references such as graphite or hard carbon. Contrary
to its oxide analogue, iron carbodiimide does not require heavy
treatments (such as nanoscale tailoring, sophisticated textures,
or coating) to obtain long cycle life with current density as high
À1
as 9 Ag for hundreds of charge–discharge cycles. Similar to
the iron compound, several other transition-metal carbodii-
mides M (NCN) with M = Mn, Cr, Zn can cycle successfully
x
y
versus lithium and sodium. Their electrochemical activity and
performance open the way to the design of a novel family of
anode materials.
M X þ ðb Á nÞ Li Ð a M þ b Li X
ð1Þ
a
b
n
where M = transition metal, X = p-group element and n =
oxidation state of X (this mechanism is detailed, for example,
in Refs. [2–6] and references therein).
The battery industry and market grow at an extremely
Transition-metal oxides of generic formula MO (M = Fe,
Ni, Co), for instance, have many advantages over others, such
as low cost, environmental benignity, and high abundance.
[
*] Dr. M. T. Sougrati, Dr. A. Darwiche, Dr. L. Monconduit,
Prof. Dr. L. Stievano
[
7]
Institut Charles Gerhardt de Montpellier, UMR CNRS 5253
Since the first report, several groups have investigated FeO
3
4095 Montpellier (France)
[8,9]
and found a low capacity retention. Many approaches tried
to overcome the shortcomings, for example, by reducing the
particle size, designing special nano-architectures, introducing
and
RØseau sur le Stockage Electrochimique de l’Energie, FR CNRS 3459
8
0039 Amiens (France)
carbonaceous composites or
a combination of these
E-mail: lorenzo.stievano@umontpellier.fr
approaches (see Ref. [9] and references therein). Neverthe-
less, such complicated processes with expensive and/or low
yield cancel out the intrinsic advantages of FeO, that is, low
cost and benignity.
Dr. X. Liu, Prof. Dr. R. Dronskowski
Institute of Inorganic Chemistry, RWTH Aachen University
5
2056 Aachen (Germany)
E-mail: drons@HAL9000.ac.rwth-aachen.de
Dr. A. Mahmoud, Dr. R. P. Hermann
JCNS and PGI, JARA-FIT, Forschungszentrum Jülich GmbH
More recently, a class of inorganic negative-electrode
conversion-reaction materials characterized by a molecular
structure has appeared, such as the well-known metal–organic
5
2425 Jülich (Germany)
Dr. A. Mahmoud
LCIS/GREENMAT, Institute of Chemistry B6, University of Li›ge
[10]
frameworks (MOF). Cyanamide/carbodiimide compounds
with the general formula M (NCN) and M = alkali, alkaline-
x
y
4
000 Li›ge (Belgium)
earth, transition metals, or metalloids are a still unexplored
family. Its best known member is the commercially available
Dr. R. P. Hermann
Materials Science and Technology Division
Oak Ridge National Laboratory, Oak Ridge, TN 37831 (USA)
[11]
fertilizer CaNCN. More recently, many other metal carbo-
[12–17]
diimides were successfully prepared.
Introducing tran-
Dr. S. Jouen
sition-metal carbodiimides was very difficult, at least until
their existence was predicted by first-principles electronic-
Groupe de Physique des MatØriaux, UMR CNRS 6634 – Normandie
University, 76801 St Etienne du Rouvray Cedex (France)
[18]
structure calculations. In fact, phases designated as MNCN
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.201600098.
(with M = Mn, Fe, Co, Ni, Cu) emerged as metastable,
5
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endothermic compounds. However, since then many transi-
tion-metal carbodiimides were prepared thanks to a variety of
[19–23]
adequate new chemical routes.
In a nutshell, carbodii-
mides are more covalent than their oxide counterparts, as it
[24]
was clearly shown for MnNCN, and the metalÀN bond is
[25]
lacking significant p interaction.
Moreover, plenty of
interesting physico-chemical properties are revealed by
comparing metal oxides with the respective carbodiimides
(
such as those shown in refs. [26–29]) and recently, copper and
cobalt carbodiimides were applied as non-oxidic water-
oxidation heterogeneous catalysts, with a dual photochemical
[30,31]
and electrocatalytic activity in neutral and basic media.
A
recent report on the use of carbodiimides in Li-ion batteries
[32]
claims that MnNCN is not electrochemically active. We will
show in the following that the latter claim is unfounded. The
aim of this work is to evaluate the potential of carbodiimides
as anode materials for Li- and Na-ion batteries. Our results
show that, indeed, Cr, Mn, Zn, and Fe carbodiimides are
electrochemically active towards Li and Na. The reaction
mechanism will be illustrated in detail for FeNCN, the
2À
equivalent of FeO in which the oxide anion O is replaced
2À
by the NCN moiety.
The synthesis and the electrochemical test conditions of
FeNCN as well as of the other studied carbodiimides are
detailed in the Supporting Information. In the same section,
the theoretical electrochemical features of FeNCN (specific
and volumetric capacity, volume expansion upon lithiation
and sodiation) are compared to those of its oxide counterpart,
FeO. The galvanostatic cycling of iron carbodiimide versus
lithium is summarized in Figure 1.
Figure 1. a) Galvanostatic profile and b) specific discharge capacity
and coulombic efficiency versus cycle number for FeNCN in a Li half-
cell. Specific discharge capacity for FeO in identical conditions is
shown in black circles.
The voltage composition profile (Figure 1a) is very
similar to that of FeO, with a first lithiation (discharge)
taking place following a plateau around 0.6–0.8 V and then
capacities of FeNCN towards Li and Na are 600 and
À1
400 mAhg , respectively, which is lower than those obtained
[
7,8]
À1
a continuous voltage decrease to 0.01 V.
The following
for the analogous oxide (750 mAhg ), in line with the higher
sweeps (first charge and second discharge) are drastically
different from the first discharge but completely reversible for
the subsequent cycles. This behavior is typical of electrode
molar mass of the carbodiimide compound. Note that these
values exceed those usually observed for common negative
electrode materials such as graphite (vs. Li) and hard carbon
(vs. Na), the latter presenting also a very large irreversible
[2,33]
materials undergoing the conversion reaction,
indicating
[37]
deep structural and morphological changes during the first
discharge, as will be shown hereafter. During the first cycle,
a significant irreversible capacity is observed, underlined by
a coulombic efficiency (CE) of about 70%. This extra
capacity can be explained, by analogy to transition-metal
oxides, in terms of electrolyte decomposition with the
formation of a solid electrolyte interphase (SEI) and a poly-
capacity at the first cycle. Moreover, the CE of the FeNCN/
Na system is excellent with a value very close to 100% after
+
the first cycle, meaning that no more Na are irreversibly
trapped during the electrolyte degradation (leading to the
increase of the SEI) during cycling.
This result is remarkable since for other negative elec-
trode materials working with both sodium and lithium, such
as Sb, the chemical nature of the SEI layer is thinner in the Li
[
34]
meric gel-type layer.
Such decomposition reactions are
[38]
favored by the formation of nanosized grains in the dis-
case than in the Na one, leading to a better CE. While the
galvanostatic behavior of FeNCN compares well to FeO, the
carbodiimide clearly exhibits improved capacity retention
versus both lithium and sodium. While the longest cycle life
[34–36]
charged electrode.
After the first discharge, the CE
reaches a higher and stable value close to 97% (Figure 1b).
During the first charge (and the following cycles), a sloping
curve is observed suggesting a single process at an average
potential of 1.4 V (arithmetic average of the two potentials
evaluated at half-charge and half-discharge), again very
similar to FeO.
reported for sophisticated FeO composites is 50–60 cycles at
À1 [7,9,39]
current densities between 50 and 400 mAg ,
non-
optimized microsized particles of FeNCN maintain a stable
capacity, noticeably higher than graphite, for more than 100
À1
For the reaction of FeNCN versus sodium, a similar
behavior is observed at a lower operating potential of 0.25 V
during the first discharge and an average operating potential
of about 1 V for the subsequent cycles (Figure 2a). At C/5
cycles at a current density of 56 mAg (C/5) versus lithium
(Figure 1b) and more than 240 cycles versus sodium (Fig-
ure 2b). Moreover, in the case of FeO/Li a decrease of about
60% of the capacity is observed after 25 cycles, whereas only
20% of the capacity is lost for FeNCN/Li after 50 cycles. An
À1
rate, that is, a current of 56 mAg , the initial reversible
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Figure 2. a) Galvanostatic profile and b) specific discharge capacity
and coulombic efficiency versus cycle number for FeNCN in a Na half-
cell.
Figure 3. Rate capability of FeNCN vs. lithium (top) and sodium
bottom). Empty and filled symbols are used for discharge and charge,
respectively.
(
additional capacity loss of only 5% is observed between the
phases. This amorphization is irreversible since no diffraction
peaks appear during the first charge or the second discharge.
To sum up, the good cycling behavior is correlated with
irreversible nanostructuration that hinders the possible iden-
tification of the phases involved in the reaction by long-range
order sensitive techniques such as XRD. We thus used
5
0th and 110th cycle. In the case of sodium, the capacity
[40]
retention is even better, similarly to the case of Sb: the
capacity loss between the 1st and the 50th charge process is
only 3%, with an additional loss of 4% after 100 cycles.
Another interesting aspect is the rate capability, shown in
Figure 3. Although the capacity is decreasing with increasing
current density, the FeNCN electrode supports well current
57
additional short-range techniques such as Fe Mçssbauer
and IR spectroscopy to overcome this issue.
À1
densities up to 9000 mAg (32C) without any irreversible
In situ Mçssbauer spectra (Figure 4) were acquired at
different cycling stages. Spectrum (a) of the initial powder is
damage when submitted to high current densities. These
observations suggest an intrinsic robustness of FeNCN as
anode material auguring that optimization of the material
morphology and fine formulation of electrodes and electro-
lyte will provide excellent performance. Finally, Zn, Mn, and
Cr analogues are also found to be electrochemically active
and present a good cycling performance as evidenced from
the preliminary tests (Supporting Information, Figure S2).
The possible application of transition-metal carbodiimides as
electrode materials for Li- and Na-ion batteries is in full
[29]
similar to that previously reported and can be fitted by two
components: the main component is a magnetic octet with
five resolved lines typical for divalent iron with a combined
quadrupolar and magnetic interaction and corresponds to
2+
antiferromagnetically ordered high-spin Fe (red curve); the
À1
weak doublet centered at 0.4 mms is attributed to slowly
3
+
[29]
relaxing Fe (gray line), as discussed by Herlitschke et al.,
which is most probably due to an impurity, such as an
amorphous oxidized Fe(NCNH) precursor.
2
[41]
accord with a previous independent study, and a patent
Spectrum (b) collected at the end of the discharge consists
[51]
À1
request has been recently filed.
of two doublets with similar isomer shifts (about 0.05 mms )
Several complementary techniques were used to elucidate
the electrochemical mechanism in this family of materials.
The reaction mechanism of FeNCN with lithium was first
investigated by operando XRD (Supporting Information,
Figure S3). A continuous decrease of the FeNCN pattern
intensity is observed along the discharge without observing
new diffraction peaks indicating the formation of amorphous
and appreciably different quadrupole splittings (0.37 and
0.87 mms ). These parameters are characteristic of super-
À1
paramagnetic iron nanoparticles usually observed at the end
of the lithiation of conversion materials, which confirms that
0
[42,43]
Li/FeNCN is most likely converted into Li NCN/Fe .
At
2
the end of the charge, spectrum (c) can only be fitted using
2+
a distribution of magnetically ordered Fe components. Thus,
5
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Figure 4. Left: Mçssbauer spectra of a a) pristine, b) discharged, and
c) charged FeNCN electrode vs. lithium. Fitted spectra obtained during
the discharge (right).
the majority of the iron-metal nanoparticles is re-oxidized in
2
À
2+
the presence of the NCN anions to give a Fe -containing
phase. The lower value of the hyperfine magnetic field
(
4 Tesla) is in agreement with the reformation of the FeNCN
phase in the form of amorphous and/or nanostructured
particles, in line with XRD data. Note that the iron oxidation
during the charge process is incomplete, since the doublets
corresponding to iron nanoparticles are still visible, albeit
very weak, at the end of the charge.
Figure 5. a) FTIR spectra for pristine powder (PP), pristine (PE), dis-
charged (D1), and charge (C1) electrodes. b),c) Zooms around the
main IR bands of the NCN group.
2
À
Ex situ FTIR spectra of the pristine and cycled electrodes
are shown in Figure 5. Pristine FeNCN displays two strong
evidenced with the zoomed spectra (Figures 5b and c).
However, the NCN stretching band is broad and shifted to
lower energies compared to pristine FeNCN, in line with the
formation of a nanostructured composite after lithium
reaction with FeNCN. Note that both cycled electrodes
contain additional absorption bands originating from the
À1
characteristic absorption bands, a narrow one at 642 cm and
À1
a broad one centered at 2050 cm corresponding to the
bending (d) and the asymmetric stretching (n ) modes of the
as
2
À
NCN ion, respectively. The symmetrical stretching mode for
the linear N=C=N group is missing because it is IR-
2À
[
19]
À
forbidden.
In the spectrum of the formulated FeNCN
electrolyte constituents, such as the PF6 anion showing an
À1
electrode, many additional bands are present between 900
intense band at 840 cm , as well as to other compounds
À1
[44,45]
[47]
and 1700 cm due to both the carbon additives
and the
formed by their partial decomposition. In summary, the
[46]
carboxymethyl cellulose (CMC) binder used for electrode
formulation. Fortunately, both carbon additives and CMC
have no absorption band in the range 1900–2200 cm , so the
complete electrochemical reaction of FeNCN with lithium
can be formulated as:
À1
main IR band of the carbodiimide is not affected. After full
lithiation, 1) the bending band (642 cm ) has disappeared
FeNCN þ 2 LiðsÞ Ð FeðsÞ þ Li NCN
ð2Þ
ðsÞ
2
ðsÞ
À1
while a new one, broader and less intense, is observed around
Analogous reactions can be proposed for the other tested
transition-metal carbodiimides, that is, MnNCN, ZnNCN, and
Cr (NCN) .
À1
6
70 cm ; and 2) the stretching band seems to consist of two
À1
unresolved bands around 1980 and 2050 cm (Figures 5b and
c). These bending and stretching bands could be the signature
2
3
This conclusive test of transition-metal carbodiimides as
of Li NCN even though their positions are slightly lower than
the bands at 690 and 2165 cm reported by Down et al. for
negative electrode materials in Li- and Na-ion batteries
showed that both divalent (iron, manganese, and zinc) and
trivalent (chromium) carbodiimides are electrochemically
active. All studied compounds show galvanostatic behaviors
similar to their oxide counterparts. Like oxides, metal
carbodiimides exhibit a typical first discharge occurring at
a low voltage pseudo-plateau with significant irreversible
2
À1
[14]
Li NCN. The difference could be related to the nanostruc-
2
tured nature of the electrode after the delithiation step.
The FTIR spectrum of the charged electrode is quite
similar to that obtained for the non-cycled electrode, espe-
cially in the range of the asymmetrical stretching band, as
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without any sophisticated pre-treatment or engineering.
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thermochemical metastability, making them very reactive
towards lithiation and sodiation. Moreover, transition-metal
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Received: January 5, 2016
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