Article

pubs.acs.org/cm

Unraveling the Structure of Iron(III) Oxalate Tetrahydrate and Its

Reversible Li Insertion Capability
Hania Ahouari,, Gwenael le Rousse,*,,,, Juan Rodrguez-Carvajal,# Moulay-Tahar Sougrati,,,
Matthieu Saubanere,,, Matthieu Courty,, Nadir Recham,*,,, and Jean-Marie Tarascon,,,

Laboratoire de Reactivite et Chimie des Solides, UMR CNRS 7314, 33 Rue Saint Leu, 80039 Amiens Cedex, France

ALISTORE - European Research Institute, FR CNRS 3104, 80039 Amiens, France

College de France, Chimie du Solide et de lEnergie, FRE 3677, 11 place Marcelin Berthelot, 75231 Paris Cedex 05, France

Sorbonne Universites - UPMC Univ Paris 06, 4 Place Jussieu, 75005 Paris, France

Reseau sur le Stockage Electrochimique de lEnergie (RS2E), FR CNRS 3459, 80039 Amiens Cedex, France
#
Institut Laue-Langevin, Avenue des Martyrs CS 20156, 38042 Grenoble Cedex 9, France

Institut Charles Gerhardt - UMR 5253, 34095 Montpellier Cedex 5, France

*
S Supporting Information

ABSTRACT: In the search for better batteries, the quest for

new positive electrode materials, which are derived from earth-
abundant elements and synthesized through low energy
demanding processes, has become an area of interest to the
scientic community. Many Liiron based polyanionic com-
pounds have already been considered for Li ion batteries, but
there still remain a large variety of Fe-based polyanionic
carboxylate compounds (carbonates, oxalates, malonates, etc.)
to be explored, among which Fe2(C2O4)3nH2O is commercially
available, but for which structure and electrochemical reactivity
toward Li are lacking. By means of combined X-ray and neutron
powder diraction, we unravel for the rst time the structure of Fe2(C2O4)34H2O. It adopts a triclinic unit cell with iron atoms
being octahedrally coordinated by one water molecule and three oxalate groups, two of them being tetradentate. This
arrangement translates into zigzag chains linked one to another through the third oxalate molecule to lead to an opened layered
structure into which two additional water molecules are located. Moreover, we demonstrate that it reacts with lithium at an
average potential of 3.35 V vs. Li leading to a sustainable capacity of 98 mAh/g. The insertionextraction of the lithium process
follows a biphasic process and involves the Fe3+/Fe2+ redox couple as deduced from in situ X-ray powder diraction and operando
Mossbauer spectroscopy measurements.

INTRODUCTION
The massive use of fossil fuels (petroleum, coal, and gas) is now
at the origin of growing economical and political concerns
because of limited reserves while the worlds need for energy is
foreseen to double within the next 20 years. Great hopes are
placed on the use of renewable energies such as wind, wave,
and solar which can generate huge amounts of electricity.
However, because of their intermittency, the use of such
energies has placed energy storage as one of the greatest
challenges of the 21st century.1 Rechargeable Li-ion batteries,
which have already conquered the portable market, are
emerging as the technology of choice for powering electric
vehicles (EVs)2,3 and show great promise for grid applications.
Aside from safety, cost and sustainability are the most
overriding factors for such applications, the reason why
LiFePO4 has become the most praised material for the next
generation of Li-ion batteries for EVs.4,5 This phase is also used
in the Limetal polymer batteries6,7 which are presently
powering the blue EV cars cruising through Paris every day,
although in that case having a Li-based polyanionic compound
is not mandatory as Li metal is used for the negative electrode.
Searching for additional sustainable Fe-based polyanionic
compounds, we have uncovered (i) a new family of Li-based
uorosulfates8,9 among which LiFeSO4F shows the highest
redox voltage (3.9 V vs. Li+/Li) ever reported for any inorganic
compound and (ii) more recently a new Li-free iron oxysulfate
having a reversible capacity of 125 mAh/g centered at 3 V.10
Aside from the inorganic polyanionic compounds, iron(II)
oxalate has already been explored as negative electrode material
via a conversion rather than an intercalation mechanism.1114
More recently, we have shown the cost-wise attractiveness of
some Fe-based phases having organic polyanions such as
Received: November 24, 2014
Revised: February 9, 2015
Published: February 12, 2015

2015 American Chemical Society 1631 DOI: 10.1021/cm5043149

Chem. Mater. 2015, 27, 16311639
Chemistry of Materials
malonates as positive electrode.15 Pursuing this survey, we
decided to study the electrochemical performance of the
iron(III) oxalate. Fe2(C2O4)36H2O is commercialized by
Sigma-Aldrich and has been so far widely used as a catalyst
for the photoreduction/oxidation reactions of dyes, organics
wastes, etc.1618 but never as an electrode to the best of our
knowledge. Let us rst recall the controversy in literature
regarding the exact amount of structural water present in
iron(III) oxalate, which is sometimes referred to as Fe2(C2O4)3
6H2O (Sigma-Aldrich), Fe2(C2O4)35H2O,19 or Fe2(C2O4)3
4.6H2O,2022 while recent chemical analyses on the commer-
cialized product are consistent with a chemical formula of
Fe2(C2O4)34H2O.23 In this paper, we conrm that the
compound contains four structural water molecules; therefore,
from now on, it will be referred to as Fe2(C2O4)34H2O.
Despite all these studies and the fact that iron oxalate has been
commercialized by Sigma-Aldrich for decades, its synthesis is
not widely reported. Moreover, to the best of our knowledge,
the structure of this crystalline material remains unknown as
stated by DAntonio et al. in 2009:23 The corresponding FeIII
compound [Fe 2 (C 2 O 4 ) 3 4H 2 O] is so far no so well
characterized, and information on its structural features is not
available.
Herein, we report a new synthesis route to prepare
Fe2(C2O4)34H2O and determine its crystal structure through
X-ray powder diraction coupled with neutron powder
diraction. We also show for the rst time that the iron(III)
oxalate compound is electrochemically active versus lithium as
it can reversibly insert 1.6 Li atoms per formula unit at 3.35 V
versus Li+/Li0.
EXPERIMENTAL SECTION
a. X-ray Powder Diraction. X-ray diraction patterns (XRD)
were collected in BraggBrentano geometry using a Bruker D8
advance diractometer with a Cu K radiation source (1 = 1.54056 ,
2 = 1.54439 ) equipped with a Lynxeye XE detector operating at 40
kV and 40 mA.
b. Mo ssbauer Spectroscopy. Mossbauer spectra were collected
at room temperature using a 0.55 Gbq source of 57CoRh in constant
acceleration mode. Absorbers were made by mixing 30 mg of the
compounds with 60 mg of boron nitride. The hyperne parameters
isomer shift (IS), line width (LW), and quadrupole splitting (QS)
were determined by tting Lorentzian lines to the experimental data,
using the MOSFIT program.
c. Neutron Powder Diraction. Neutron powder diraction was
performed on the D20 powder diractometer at ILL (Institut Laue
Langevin, Grenoble) in its high resolution mode (takeo angle 120)
with a wavelength of = 1.35821 obtained with a germanium (117)
monochromator. The powder was placed in a 6 mm diameter
vanadium cylindrical container.
d. Electrochemical Characterization. The electrochemical tests
were carried out using Swagelok type cells. The positive electrode
composite was prepared by mixing 70 wt % of active material with 30
wt % of Ketjenblack carbon (as electronic conductor) using a Spex-800
unit for 8 min under argon atmosphere. The cells were assembled in
an argon-lled glovebox by using 46 mg/cm2 of the previous
composite as positive electrode separated from the negative electrode
(lithium disk) by 2 sheets of glass ber disks (Whattman GF/D
borosilicate), the whole setup being soaked in a LiPF6 (1 M) solution
of ethylene carbonate (EC)/dimethyl carbonate (DMC) mixture (1/1
w/w). Galvanostatic dischargecharge tests were conducted with a
MacPile (Claix, France) controller at a constant temperature of 25 C.
The cells were cycled between 2.5 to 3.9 V vs. Li+/Li0 at a C/10 rate (1
Li+ exchanged per 10 h).
e. DFT Calculations. Periodic DFT+U calculations were
performed using the VASP code24,25 and the projector-augmented-
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wave (PAW) method of Blochl.26 The exchange-correlation energy
was described by the functional of Perdew, Burke, and Ernzerhof
(PBE)27 and the Hubbard corrections28 were made using a Ueff for Fe
equal to 4.0 eV. Long-range dispersion corrections have been taken
into account within a DFT-D2+U approach of Grimme,29 DFT-
D3+U30,31 as implemented in Vasp.32 Gibbs energy of bulk phases at
nite temperature are obtained following the quasiharmonic
approximation33 while for the gas phases they are obtained by adding
the DFT energy, the zero point energy, the mean rotational and
translational contribution, and the entropic term taken from the
JANAF reference.
RESULTS
The earlier report on the synthesis of greenish powdered
Fe2(C2O4)34H2O dated back from 1993. Galwey et al.21 have
obtained this compound (whose chemical assignment was
Fe2(C2O4)34.6H2O) by precipitation of a solution containing
a mixture of ferric hydroxide and oxalic acid. Herein we
deviated from this process by using a nitrate rather that an iron
hydroxide precursor. More specically the phase was prepared
by complete evaporation in an oil bath at 80 C under a
continuous stirring of 10 mL of a concentrated water solution
of H2C2O42H2O and Fe(NO3)39H2O precursors with 3:2
molar ratio. The glass vial containing the solution was covered
with an aluminum foil to prevent the photoreduction in water
of iron(III) oxalate complex into iron(II) oxalate. Its X-ray
powder diraction (XRD) pattern is analog to the one
produced by commercial Fe2(C2O4)34H2O powders (Sigma-
Aldrich) with however a higher degree of crystallinity.
Mossbauer spectrum (Figure 1a) indicates that iron is present
in a unique environment with an isomer shift of 0.38 mm/s and
a quadrupole splitting of 0.40 mm/s, suggesting a high spin
Fe3+ in octahedral coordination in agreement with the
literature.20,23 TGA conducted under air (Figure 1b) conrmed
that iron(III) oxalates contain only four water molecules (64%
weight loss according to the reaction Fe2(C2O4)34H2O(s) +
3/2O2(g) Fe2O3(s) + 6CO2(g) + 4H2O(g)). Thus, being
condent on the purity of the powder, an overnight XRD scan
in high resolution conguration was collected in view of solving
the crystal structure. The resulting XRD pattern presents many
Bragg peaks, the rst one appearing at low 2 angle (2 =
9.76, d = 9.07 ) is indicative of a low symmetry/large unit
cell. The best way to solve a crystal structure is usually by
recording single crystal X-ray diraction, but we never
succeeded in growing single crystals. Moreover, our attempts
to record synchrotron X-ray powder diraction pattern failed
because the sample was not stable under beam. Therefore, we
embarked into an ab initio structural determination from
coupled X-ray and neutron powder diraction data.
The X-ray pattern (Figure 2, top) presents many sharp Bragg
peaks proving that iron(III) oxalate is well crystallized, even
though at high angles (above 5060) the peaks are clearly
broadened as a result of strain whose induced broadening varies
as tan . The Bragg peaks were indexed with the Dicvol
program34 in a triclinic unit cell with the following lattice
parameters: a = 5.306(1) , b = 6.637(1) , c = 9.138(1) ,
= 91.79(1), = 97.58(1) and = 93.32(1). This cell
presents a volume of 318.2(1) 3 which can accommodate one
formula Fe2(C2O4)34H2O. The space group was naturally
chosen as P1, because the oxalate groups naturally present an
inversion center.
The structure was solved in two successive steps: rst from
X-ray diraction to get the positions of the heavy atoms and
then neutron diraction to locate water molecules and
DOI: 10.1021/cm5043149
Chem. Mater. 2015, 27, 16311639
Chemistry of Materials
Figure 1. (a) Room temperature 57Fe Mo ssbauer spectra of
Fe2(C2O4)34H2O. (b and c) TGA curve decomposition coupled
with mass spectroscopy for Fe2(C2O4)34H2O carried under air (b)
and under argon (c).
Figure 2. Combined Rietveld renement of X-ray powder diraction
pattern (RBragg = 4.69%, %, Rp = 11.4%, 2 = 2.36) and neutron
diraction for Fe2(C2O4)34H2O (RBragg = 2.25%, Rp = 7.61%, 2 =
2.36). The red circles, black continuous line, and bottom dark gray line
represent the observed, calculated, and dierence patterns, respec-
tively. Vertical blue tick bars are the Bragg positions allowed in the
triclinic P1 cell.
complete the structural model. The rst step (against X-ray
diraction data) was done using the EXPO software35 with two
approaches considered: (1) phasing by direct methods and (2)
using the newly developed RAMM method.36 The two
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approaches led to consistent structural models although
incomplete and/or approximate (in particular relative to the
oxalate groups), therefore the structure was nally completed
using successive Rietveld renements37 and Fourier dierence
maps performed using the FullProf suite of programs.38 The
second step was to measure the same sample on a neutron
powder diractometer, to take advantage of the dierent
contrast neutrons oer as compared to X-rays: bFe = 9.45 fm,
bC = 6.646 fm, bO = 5.803 fm, bH = 3.739 fm. A correction
was applied to take into account the absorption and the
eective absorption due to incoherent scattering of hydrogen
atoms (R = 0.3669). The water molecules were rst treated as
rigid bodies, their orientation was deduced from simulated
annealing techniques39 using the FullProf program,38 and then
each hydrogen atom was freely rened. The nal structural
model (Table 1) was obtained from a combined X-ray/neutron
Rietveld renement without any constraints. Note that some
preferred orientation in the [010] direction as well as
anisotropic strain broadening was rened in the case of the
X-ray pattern.
The nal X-ray and neutron renements are shown in
Figure 2. All atoms are placed into the general Wycko position
2i, so that there is only one crystallographic site for iron atoms,
in agreement with the Mossbauer spectrum (Figure 1a).
Figure 3a shows the atomic positions within a unit cell. Iron
atoms are located in the middle of an octahedron (FeO
distances ranging from 1.92 to 2.09 ) typical for Fe3+. Out of
the six oxygen ligands, ve are part of an oxalate molecule
whereas the sixth one (O7) belongs to one water molecule.
Each oxalate group is placed at the inversion centers of the unit
cell, i.e., at (0, 0, 0), (1/2, 1/2, 1/2), and (1/2, 1/2, 0) for C1,
C2, and C3, respectively, so that only three crystallographic
sites are necessary to describe them (one carbon and two
oxygen sites); lastly, O8, H81, and H82 constitute the second
water molecule. The water molecules are oriented in such a way
that hydrogen bonding between hydrogen and oxygen atoms is
possible as highlighted in Figure 3b (OH distances in the
range 1.72.1 ).
The structural model, which is consistent with the expected
formula Fe2(C2O4)34H2O, is plotted in Figure 4 along
dierent crystallographic directions. FeO6 are linked one to
each other through two tetradentate oxalate molecules (built on
C2 and C3) to form innite zigzag chains running along [001]
(Figure 3c). These chains are connected through the third
bidentate oxalate (built on C1) to form corrugated layers
corresponding to the (1, 1, 0) planes, stacked along the
[110]* direction (Figure 4b). It results that Fe2(C2O4)34H2O
presents an opened structure. This structural feature combined
with the presence of Fe3+ was a motivation to embark into an
electrochemical reactivity of this phase toward Li and eventually
Na, as described next.
The voltage versus composition prole for a Li/Fe2(C2O4)3
4H2O cell is shown in Figure 5. It reveals the presence of a
plateau centered at around 3.35 V vs. Li+/Li0 as conrmed by
the corresponding dx/dV curve (Figure 5, right panel). During
the rst discharge, about 1.8 Li+ per formula unit are inserted in
the structure whereas 1.6 Li+ ions are removed from the
structure upon the subsequent charge leading to a steady
capacity retention of about 98 mAh/g which represents nearly
80% of the theoretical capacity (CTheo = 122 mAh/g).
Subsequent discharge/charge cycles superimpose well over
more than 10 cycles as seen in the Figure 5 inset.
DOI: 10.1021/cm5043149
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Table 1. Structural Parameters for Fe2(C2O4)34H2O, Deduced from the Coupled Rietveld Renement of the X-ray and Neutron
Diraction Patterns
space group P1
a () 5.3065(1)
b () 6.6373(1)
c () 9.1381(1)
(deg) 91.793(1)
(deg) 97.583(1)
(deg) 93.323(1)
V (3) 318.26(1)
Z 1
density (g/cm3) 2.337
atom Wycko position x y z B (2)
Fe 2i 0.4767(6) 0.2932(4) 0.2402(4) 0.95(7)
C1 2i 0.1217(11) 0.0709(9) 0.0116(7) 1.17(11)
C2 2i 0.3783(11) 0.4393(8) 0.5137(7) 0.67(9)
C3 2i 0.3823(10) 0.5561(8) 0.0121(6) 0.85(9)
O1 2i 0.2081(13) 0.1577(9) 0.9074(8) 1.68(13)
O2 2i 0.2318(12) 0.0869(8) 0.1491(6) 1.44(14)
O3 2i 0.2838(11) 0.3073(8) 0.4159(7) 0.75(9)
O4 2i 0.2906(12) 0.4803(9) 0.6345(7) 1.17(11)
O5 2i 0.2927(10) 0.5127(8) 0.1302(7) 0.87(10)
O6 2i 0.7050(12) 0.3227(9) 0.0780(8) 1.66(15)
O7 2i 0.6917(14) 0.0816(9) 0.3325(9) 2.00(15)
H71 2i 0.784(3) 0.113(2) 0.4312(19) 4.3(3)
H72 2i 0.786(3) 0.008(2) 0.2640(16) 4.1(3)
O8 2i 0.1614(15) 0.7980(11) 0.3891(8) 2.23(16)
H81 2i 0.202(2) 0.8495(19) 0.3011(15) 2.8(3)
H82 2i 0.001(2) 0.698(2) 0.3548(16) 3.6(3)

Figure 3. (a) Representation of a unit cell content: Fe is blue, C is gray, H is purple, and oxygen atoms part of oxalate molecules and water molecules
are red and pink, respectively. Labels for C are indicated for clarity. (b) Illustration of the hydrogen bonding. (c) FeO6 are linked one to each other
through two tetradentate oxalate molecules to form innite zigzag chains running along [001].

To grasp further insight into the mechanism of the Li
insertion/extraction process in Fe2(C2O4)34H2O, in situ XRD
measurements were carried out using an homemade electro-
chemical cell equipped with a beryllium window.40 Figure 6
shows the XRD patterns collected for every change in x of 0.1
as a Li/Fe2(C2O4)34H2O cell being discharged and charged at
C/20 rate. On discharge, we observe the disappearance of the
diraction peaks of the pristine material at the expense of new
1634
peaks that become unique at the end of the discharge
(Li1.8Fe2(C2O4)34H2O) which indicates a biphasic insertion
process. Upon charge, the reverse phenomenon occurs.
Moreover, the XRD pattern of the fully charged material nicely
superimposes with that of the pristine material, indicating a
fully reversible Li-insertiondeinsertion process. Despite the
bad quality of intensities induced by the beryllium window, we
have been able to rene the pattern recorded at the end of the
DOI: 10.1021/cm5043149
Chem. Mater. 2015, 27, 16311639
Chemistry of Materials Article

Figure 4. Structure of Fe2(C2O4)34H2O viewed perpendicular to the [010], [110], [100], and [001] directions. Notice that, in the [100] direction,
we can see the zigzag chain formed through FeO6 octahedra linked to two tetradendate oxalate molecules (denoted Ox in the gure). Fe is blue, C
is gray, H is purple, and oxygen atoms part of oxalate molecules and water molecules are red and pink, respectively.

Figure 5. Voltage versus composition prole for Fe2(C2O4)34H2O cycled at C/10 together with the corresponding derivative x/V curve (right).
Capacity vs cycle number is given as inset.

Figure 6. In situ XRD patterns obtained for Fe2(C2O4)34H2O cycled

at C/20. Patterns have been collected every 2 h.

discharge with the same triclinic cell as the pristine one (whose
renement is shown Figure 7, top), with lattice parameters
a = 5.400(1) , b = 6.584(1) , c = 10.011(1) ,
= 96.01(1), = 101.21(1), = 94.58(1), and a cell
volume of 345.4(1) 3 (Figure 7, bottom). The result of the Figure 7. Portion of the Rietveld renement of the XRD patterns
renement suggests that the structure framework of the pristine collected in situ for pristine Fe2(C2O4)34H2O and at the end of
discharge Li1.8Fe2(C2O4)34H2O. Deduced lattice parameters and unit
triclinic Fe2(C2O4)34H2O phase is maintained upon lithiation, cell volumes are indicated.
which is merely accompanied by a volume expansion of 8.4%,
which is in same order of magnitude as LiFePO4 (7%).
The reversibility of the Li uptake-removal process was further collected during discharge and charge of the compound at
conrmed by operando Mossbauer measurements (Figure 8) C/10 rate using a stainless steel Swagelok-type cell.40 The
1635 DOI: 10.1021/cm5043149
Chem. Mater. 2015, 27, 16311639
Chemistry of Materials
Figure 8. Operando room temperature 57Fe tted Mossbauer spectra
of Fe2(C2O4)34H2O recorded during the electrochemical process at
C/10 rate together with the voltage composition curve.
spectra recorded for 3 h between 4 mm/s during the cell
discharge show a narrow doublet corresponding to Fe3+ which
progressively disappears while a new doublet typical of Fe2+
(isomer shift of 1.17 mm/s and a quadrupole splitting of
1.93 mm/s) appears and becomes predominant at the end of
discharge. During the subsequent charge up to 3.9 V, the
reverse phenomenon was observed with almost all the Fe2+
returning to its +3 state upon oxidation. The intermediate
Mossbauer spectra recorded during the rst discharge and
subsequent charge can all be tted using a linear combination
of the Fe2+ doublet and the Fe3+ doublet, as illustrated in
Supporting Information, Figure S1.
For the sake of completion, we tested the electrochemical
behavior of Fe2(C2O4)34H2O versus Na. The voltage
composition curve (not shown here) indicates that around
1.3 Na per formula can be inserted at around 3.0 V vs. Na,
which is in agreement with the usual 300 mV dierence
Figure 9. Comparison between iron coordination in humboldtine (FeC2O42H2O) and Fe2(C2O4)34H2O. The color code used is the same as in
Figure 2.
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observed between Na and Li. However, huge polarization and
very poor cyclability prevent the use of this material as
electrode for Na batteries.
DISCUSSION
We have reported the structural determination of iron(III)
oxalate tetrahydrate, which constitutes a model case of what can
be achieved in terms of structural determination from powder
diraction. Since the X-ray powder pattern of this phase is
dominated by iron, we had to use neutron diraction as a
complementary technique to univocally locate oxalate groups
and water molecules. Interestingly, Fe2(C2O4)34H2O which
crystallizes in a triclinic unit cell presents some features already
observed in the ferrous oxalate Fe(C2O4)2H2O. The latter is a
mineral called humboldtine, which exists in two forms, one
monoclinic and one orthorhombic, both built on innite chains
made of Fe and tetradentate oxalate molecules. The main
dierence between humboldtine and Fe2(C2O4)34H2O is that
in the former iron is coordinated to four oxygen atoms being
part of two oxalate groups and two water molecules, while in
the latter only one water molecule coordinates iron and a third
oxalate ligand bridges chains one to each other to form layers
(Figure 9). Moreover, note that two of the four water
molecules are linked only by hydrogen bonds within the
Fe2(C2O4)34H2O phase. This motivated us to explore the
feasibility of removing these two water molecules to form
Fe2(C2O4)32H2O so as to decrease its weight and thereby
increase its electrochemical capacity.
Figure 1b shows the TGA prole collected under air with
namely a major loss occurring in two steps between 150 and
250 C corresponding to the departure of water and carbon
dioxide as deduced by mass spectroscopy measurements. This
implies the occurrence of a simultaneous dehydration
decomposition and the concomitant formation of iron oxide
Fe2O3 as conrmed by XRD measurements. When such
measurements are performed under argon, we observe a similar
weight loss at 400 C with however a spreading of the
temperature range (150380 C) over which the dehydration
DOI: 10.1021/cm5043149
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Figure 10. (a and b) Structure of the discharged phase Li2Fe2(C2O4)34H2O as deduced by DFT+U and DFT-D2+U calculations, viewed along the
[010] and [100] directions. Fe octahedra and Li tetrahedra are in blue and green, respectively. (c) Illustration of the hydrogen bonding using the
same orientation as in Figure 3b for the pristine material.
and a decomposition into CO2 and CO are taking place as
determined by mass spectroscopy measurements. However, the
formation of a certain amount of ferrous oxalate was observed
during the rst loss and corresponds to the thermal
decomposition of ferric oxalates in an inert atmosphere as
conrmed by Mossbauer spectroscopy. This reduction of FeIII
to FeII is ascribed to the electron transfer during oxidation of
the oxalate group to CO2 (C2O42 2CO2 + 2e) yielding
two electrons that consecutively reduce FeIII cations.20 The
carbon monoxide released during the second loss comes from
the decomposition of FeC2O4 (FeC2O4(s) FeO(s) + CO(g) +
CO2(g)). At the end of the decomposition (400 C), a mixture
of iron oxides (Fe3O4, FeO) were formed, which nearly
accounts for the 65% weight loss measured. Whatever the
details, it results that the preparation of the dehydrated oxalate
phase is not possible in the described conditions and we believe
that it is a direct consequence of the strong hydrogen bonding
depicted previously.
Lastly, we embarked into DFT calculations to (i) obtain
further insights about the Li positions in the discharged state,
(ii) check whether the orientation of the water molecules
determined from neutron diraction was the most energetically
stable, and (iii) validate the nonstability of the partially or fully
dehydrated compounds.
The crystal structure of Fe2(C2O4)34H2O is perfectly
reproduced by the DFT + U method provided that van der
Waals interactions are included (Supporting Information,
Figure S2 and Table S1) and is shown to be dynamically
stable (Supporting Information, Figure S3). By adding the van
der Waals interaction term, we could conrm that the solved
structure with the hydrogen belonging to water molecules and
pointing to oxygen atoms was the most stable conguration.
Pursuing further into these calculations, we tried to position the
Li ions into the fully lithiated Li2Fe2(C2O4)34H2O phase as we
could not access this information from XRD or neutron
techniques due to our inability to prepare sucient powder
amounts of Li2Fe2(C2O4)34H2O via chemical reducing agents.
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Because strongly electrostatic interactions are expected
between the Li+ ions and the oxygen ligands, calculations
have been performed with and without dispersion corrections.
The most probable Li-sites, from structural considerations (e.g,
tetrahedral sites), have been guessed prior to fully relaxing the
structure based on (i) the unit cell parameters starting from
those obtained by the renement of the in situ XRD data
and (ii) the preassigned Li atomic positions for
Li2Fe2(C2O4)34H2O. Whatever the dispersion considerations
(DFT+U, DFT-D2+U, DFT-D3+U) we have tried, we
obtained similar structures (Figure 10 and Supporting
Information, Table S2), providing condence about the
robustness of our results. It turns out that the inserted
Li-ions occupy tetrahedral sites at (0.176, 0.796, 0.201) which
are built from three oxygen atoms of the oxalate ligands and
one water molecule. More descriptively one oxalate ligand
bridges Li in a tetradentate way. Interestingly, as compared to
the delithiated pristine phase, water molecules undergo a
rotation to coordinate to the Li-centered tetrahedra, therefore
losing their weak hydrogen-bonds with the oxalate network,
while new ones are created (Figure 10c). Such a Li-driven water
molecule rotation enlisting the breaking and formation of van
der Waals hydrogen interactions is of weak energy, and this is
consistent with the voltagecomposition curve which shows a
limited polarization between charge and discharge. Metal
oxygen bonds breaking in contrast leads to humongous
polarization voltages as reported for conversion reactions.
During the course of this investigation, we also computed
using the DFT+U approach the average redox potential
associated with the Li insertion reaction [Fe2(C2O4)34H2O +
2Li Li2Fe2(C2O4)34H2O] and found a value of 3.4 V, which
is in good agreement with the experimental value (3.35 V).
This redox potential value falls within the same range of values
reported for numerous iron based polyanionic compounds
(Figure 11) and is positioned between the potential of the
sulfates and phosphates among which LiFePO4 (3.45 V vs. Li)1
is the most studied and attractive application-wise. The C2O42
species, being less electronegative than PO43 and SO42
DOI: 10.1021/cm5043149
Chem. Mater. 2015, 27, 16311639
Chemistry of Materials
Figure 11. Comparison between the average potential of dierent
polyanionic compounds used as positive electrode for Li bat-
teries.1,41,4345 LiFeSO4FTri and LiFeSO4FTavo refer to the triplite
and tavorite forms of LiFeSO4F, respectively.
polyanions, one would expect a lower potential. This reminds
us that the inductive eect can literally be applied for materials
solely sharing the same structure.
Lastly, turning back to the nonstability of the hypothetical
dihydrated Fe2(C2O4)32H2O phases, we calculated within
the DFT-D3+U formalism the energy associated with the
removal of the two molecules of water at T = 0 K: E(H2O) =
E[Fe2(C2O4)34H2O] (E[Fe2(C2O4)32H2O] + 2E[H2O]).
We found this reaction to be endothermic (E(H2O) =
1.6 eV), which is about two times the vaporization energy of
water: 0.42 eV/water molecule), implying that the water
molecules, although not covalently bonded to the network,
strongly stabilize the structure through combination of
electrostatic and van der Waals interactions (Supporting
Information, Table S3). The eect of temperature was then
considered, with H2O coming out of the structure in a gaseous
form so that an entropy term was added to our calculations.42
The corresponding temperature-dependent phase diagram at
ambient pressure G(H2O[P,T]) in air plotted versus T is shown
in Figure 12 with G(H2O[P,T]) is dened as
G(H2O[P , T ]) = G[Fe2(C2O4 )3 4H 2O]
{G[Fe2(C2O4 )3 2H 2O] + 2G[H 2O]}
It indicates that the following hypothetical Fe2(C2O4)3
2H2O + two water molecules in the gaseous state system
presents a lower energy than Fe2(C2O4)34H2O when the
temperature is increased above 250 C. However, at this
temperature Fe2(C2O4)34H2O is already decomposed; there-
fore, these calculations explain our inability to remove two
water molecules from the parent tetrahydrate oxalate phase
without destroying the structure.
CONCLUSIONS
We have solved from combined neutron/X-ray experiments the
structure of Fe2(C2O4)34H2O and shown the ability of this
phase to reversibly insert 1.6 Li per formulae unit with a plateau
at around 3.35 V vs. Li, leading to a sustained capacity of 98
mAh/g. Complementary in situ XRD and Mossbauer spectros-
copy measurements have conrmed the occurrence of an
electrochemical activity via a biphasic insertion process, linked
to the Fe3+/Fe2+ redox couple.
1638
Article
Figure 12. Temperature and pressure dependent phase diagram
computed with dispersion correction within the DFT-D3+U formal-
ism for water release from the Fe2(C2O4)34H2O to form Fe2(C2O4)3
2H2O. The water molecules removed from the structure are those
which are not directly bonded to iron.
Among the few reported 3d-metal based organic intercalation
compounds, this oxalate phase compares favorably in terms of
voltage and capacity to the metal organic framework phase
MIL-53(Fe) (LixFeIIxFeIII1x(OH)0.8F0.2L with
L = O2CC6H4CO2, 75 mAh/g at 3 V).43 Iron oxalate presents
a nearly identical energy density as the recently reported
carbonophosphate Li3FePO4CO344,45 because its lower specic
capacity (98 mAh/g versus 110 mAh/g) is compensated by its
higher voltage (3.35 V versus 3 V). Moreover, Fe2(C2O4)3
4H2O is commercially available, and there is room to improve
its capacity to the theoretical one (122 mAh/g). This approach
is an attractive path toward the quest for inexpensive,
environmental friendly positive electrode materials for large
volume applications such as grids where weight is not a penalty.
*
ASSOCIATED CONTENT
S Supporting Information
CIF le of Fe2(C2O4)34H2O. Fit of the Mossbauer spectra
recorded on discharge and charge. Structure of the relaxed
Fe2(C2O4)34H2O as obtained with DFT-D3+U. Structural
parameters of relaxed Fe2(C2O4)34H2O and Li2Fe2(C2O4)3
4H2O using DFT+U, DFT-D2+U, DFT-D3+U, DFT-HS+U.
Stability energy of water molecules E(H2O) obtained using
DFT+U, DFT-D2+U, DFT-D3+U, and DFT-TS+U. This
material is available free of charge via the Internet at http://
pubs.acs.org.
AUTHOR INFORMATION
Corresponding Authors
*Gwenaelle Rousse. E-mail: gwenaelle.rousse@college-de-
france.fr.
*Nadir Recham. E-mail: nadir.recham@u-picardie.fr.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
We are grateful to the French national computing center
(CINES Grant cmm6691) and to the computer center of the
Institut Charles Gerhardt in Montpellier (ICG, France). The
authors would like to thank the ALISTORE-ERI nanopositive
team for the fruitful discussion. H.A. acknowledges ALIS-
TORE-ERI for her Ph.D. grant.
DOI: 10.1021/cm5043149
Chem. Mater. 2015, 27, 16311639
Chemistry of Materials Article

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1639 DOI: 10.1021/cm5043149

Chem. Mater. 2015, 27, 16311639