Electrochemical and Solid-State Letters, 12 共4兲 A91-A94 共2009兲 A91

1099-0062/2009/12共4兲/A91/4/$23.00 © The Electrochemical Society

Crystallite Size Control and Resulting Electrochemistry

of Magnetite, Fe3O4
Shali Zhu,a Amy C. Marschilok,b,* Esther S. Takeuchi,a,b,c,* and
Kenneth J. Takeuchia,z
a
Department of Chemistry, bDepartment of Electrical Engineering, and cDepartment of Chemical
and Biological Engineering, University at Buffalo (SUNY), Buffalo, New York 14260, USA

As an environmentally benign, superparamagnetic material, magnetite 共Fe3O4兲 has been a topic of interest for applications ranging
from drug delivery to data storage. We report here investigation of magnetite as a lithium-battery material. While Fe3O4 synthesis
has been widely studied, our approach afforded excellent crystallite size control without constraining media or elaborate equip-
ment. Upon electrochemical testing, a strong correlation between performance and crystallite size was observed, resulting in a
⬃30% capacity increase. To the best of our knowledge, this is the first study of electrochemical effects of Fe3O4 crystallite size
where all nanocrystalline samples were prepared using the same method.
© 2009 The Electrochemical Society. 关DOI: 10.1149/1.3078076兴 All rights reserved.

Manuscript submitted December 8, 2008; revised manuscript received January 12, 2009. Published February 9, 2009.

Iron-containing electrode batteries have been studied historically
as anodes and, more recently, as cathodes for primary and secondary
batteries.1 Due to their low cost and environmentally friendly nature,
iron oxides are especially attractive battery-electrode materials. His-
torically, interest in Fe3O4-based electrodes grew out of a desire to
develop an alternative electrode material to FeS2 for high-
temperature batteries.2 In the 1980s, Thackeray and co-workers
completed significant early work associated with the development
and characterization of high-temperature and room-temperature
Fe3O4-based batteries.2-4
More recently, there has been a resurgence of interest in this
material, with a few electrochemical studies involving nanocrystal-
line Fe3O4. Thin-film nanocrystalline magnetite and magnetite-
based composites have been investigated.5-7 The capacitance of thin
film and powdered nanocrystalline magnetite has been reported.8,9
Sivakumar et al. utilized Fe2O3−x thin films grown by pulsed laser
deposition and commercial Fe3O4 nanoparticles with a mean size of
65 nm vs lithium metal electrodes.10,11 Cells were discharged at cur-
rent densities of 2–40 ␮A/cm2. Changes in magnetic and X-ray
characteristics on discharge were studied, where a smaller decrease
in saturation magnetization for thin films vs nanoparticles was at-
tributed to kinetic effects. Ito and co-workers prepared 20 nm Fe3O4
particles and tested these in lithium batteries at room temperature
and at 60°C.12 When discharged at 0.1 mA/cm2 to a terminal volt-
age of 1 V, 400 mAh/g was delivered at room temperature, while
⬎500 mAh/g was delivered on 60°C testing. The addition of india
ink or polyvinyl alcohol was found to further improve the battery
discharge characteristics. When tested as secondary batteries, cycla-
bility was maintained through three charge–discharge cycles. Ko-
maba and co-workers recently reported the first investigation of the
crystallite size effect of nanocrystalline Fe3O4 for rechargeable
lithium batteries.13 Fe3O4 powders with average particle sizes of
400, 100, and 10 nm, and Brunauer–Emmett–Teller surface areas of
6.6, 50, and 155 m2 /g, respectively, were prepared using different
techniques and utilized as electrode materials vs lithium-metal
counter and reference electrodes. Crystallite size had a significant
impact on the first discharge capacity, where the 10 nm sample de-
livered 130 mAh/g to 1.5 V in Li+ electrolyte, while the 400 nm
sample delivered only 7 mAh/g. The nanocrystalline 10 nm sample
also showed good performance in Na+ electrolyte, delivering
160 mAh/g to 1.5 V on the first cycle. Good capacity retention was
observed in the nanocrystalline sample over 30 charge/discharge
cycles.
We report here the investigation of Fe3O4 as a battery electrode
material for lithium primary batteries. Notably, all of our nanocrys-
* Electrochemical Society Active Member.
z
E-mail: takeuchi@buffalo.edu
talline Fe3O4 materials were synthesized using the same technique,
allowing a direct evaluation of crystallite-size impacts on electro-
chemistry without any complicating factors. Upon electrochemical
testing, a strong correlation between performance and crystallite size
was observed, resulting in a significant ⬃30% capacity increase
across the Fe3O4 crystallite range studied.
Experimental
A coprecipitation method was used to prepare magnetite
共Fe3O4兲. Stoichiometric mixtures of iron共III兲 chloride hexahydrate
共FeCl3·6H2O兲 and iron共II兲 chloride tetrahydrate 共FeCl2·4H2O兲 were
dissolved in varying volumes of degassed water. The resulting solu-
tion was added dropwise to a roundbottom flask containing a stirred
solution of degassed water and triethylamine 关N共CH2CH3兲3兴. The
roundbottom flask was submerged in an ice bath throughout the
synthesis to control the reaction temperature. In addition, the stirring
rate and addition rate were held constant for all reactions at
1000 rpm and 2 s/drop, respectively. Samples were isolated using a
Eppendorf 5804 Centrifuge, operating at 7000 rpm, and washed
with deionized water. Powdered samples were dried in vacuo at
60°C. Samples were ground using a ceramic mortar and pestle and
passed through a 230 mesh sieve prior to characterization.
The material was then characterized by X-ray powder diffraction
共XRD兲. A Rigaku Ultima IV X-ray powder diffractometer was used
for XRD analysis. Cu K␣ radiation was utilized with Bragg–
Brentano focusing geometry. MDI JADE version 8.5.3 software
with International Centre for Diffraction Data and National Institute
of Standards and Technology databases was used for search-match
analysis. Peak Fit software from Seasolve Software, Inc., was used
to measure the full width at half-maximum of the 共311兲 peak. Crys-
tallite sizes were determined using the Scherrer equation after cor-
recting for instrumental broadening using a LaB6 standard pur-
chased from Gem Dugout.
Cyclic voltammetry 共CV兲 data was collected inside an argon-
filled glove box using a CHI 604B electrochemical analyzer. The
working electrode was constructed using a 2 mm diameter platinum
electrode coated with a thin layer Fe3O4, graphite, and polyacrylic
acid mixture. A three electrode assembly was used, with lithium
metal reference and counter electrodes, in an electrolyte of 1 M
LiAsF6 in 50/50 共v/v兲 propylene carbonate/dimethoxyethane. An
initial and final voltage of 2.5 V, a lower limit voltage of 0.9 V, and
scan rates of 2.00, 4.00, or 6.00 ⫻ 10−5 V/s were used.
Cathode pellets were prepared by mixing 40% Fisher 38 graph-
ite, 10% poly共tetrafluoroethane兲 powder and 50% Fe3O4. Cathode
pellets were pressed at 6 tons/cm2. Type 2325 coin cells were fab-
ricated within an argon-filled glove box utilizing coin-cell parts and
assembly equipment obtained from the National Research Council

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 A92 Electrochemical and Solid-State Letters, 12 共4兲 A91-A94 共2009兲
Figure 1. Powder XRD of Fe3O4: 共A兲 6.2, 共B兲 8.2, and 共C兲 9.6 nm crystallite
size.
of Canada. Electrolyte of 1 M LiAsF6 in 50/50 共v/v兲 propylene
carbonate/dimethoxyethane was used along with a lithium-metal an-
ode.
Coin cells were discharged using a Bitrode SCN Cycle Life
Tester battery testing unit. A constant temperature of 20°C was
maintained during discharge. Cells were discharged under a
constant-current test protocol which involved intermittent higher
current pulses. Multiple current densities and intermittent pulsing
were used in this test to understand the behavior of the Li/Fe3O4
cells under multiple usage regimes. Because 0.08 mA/cm2 was the
lowest current density utilized, and it was used for the majority of
the test, all voltage measurements made during steps 1 and 3 were
termed background voltage measurements. For step 1, the cells were
discharged for 2 h at a 0.08 mA/cm2 current density. During step 2,
a 2 mA/cm2 current, 5 s pulse was applied. During step 3, the cells
were discharged for 2 h at a 0.08 mA/cm2 current density. During
step 4, a 5 mA/cm2 current, 5 s pulse was applied. This four-step
sequence was repeated to fully discharge the cells. Testing was sus-
pended when the background voltage dropped below 1.0 V.
Results and Discussion
Material characterization.— XRD patterns were recorded of the
magnetite 共Fe3O4兲 samples prepared in our laboratories, as shown in
Fig. 1. The patterns showed excellent correspondence to a literature
pattern of Fe3O4, with no extra peaks observed in our data.14 Crys-
tallite sizes of the Fe3O4 powders were determined by applying the
10
9
crystallite size (nm)
8 B
7
6
y = 55.76x + 6.31
R2 = 0.86
5
0 0.01 0.02 0.03 0.04 0.05
Fe2+ concentration (M)
Figure 2. Average Fe3O4 crystallite size vs Fe2+ concentration.
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3.5
A
3.0
B
C
2.5
voltage (V)
2.0
1.5
1.0
0.5
0.0 0.5 1.0 1.5 2.0 2.5
x in LixFe3O4
Figure 3. Background voltage 共during 0.08 mA/cm2 discharge兲 of Li/Fe3O4
batteries containing 共A兲 6.2, 共B兲 8.2, and 共C兲 9.6 nm crystallite-size Fe3O4.
Scherrer equation15,16 to the 共311兲 peak of the XRD data. A strong
correlation among Fe3O4 crystallite size and concentration was ob-
served, as shown in Fig. 2, where more concentrated solutions re-
sulted in larger Fe3O4 crystallite sizes. Multiple Fe3O4 samples were
prepared at each concentration, and the data shown are the average
crystallite sizes for each concentration studied. Reactant solution
concentration of other Fe2+ and Fe3+-containing reagents has been
previously shown to impact Fe3O4 crystallite size.17-19
Electrochemical evaluation.— Magnetite samples with small
共6.2 nm兲, intermediate 共8.2 nm兲, and large 共9.6 nm兲 crystallite sizes
were selected for further electrochemical evaluation and utilized for
cathode-pellet fabrication and coin-cell assembly as described
above. On discharge at room temperature, the voltage shows a
gradual decrease from an initial potential of 3.3 V, as shown in Fig.
3. Cells made using the two larger crystallite-size Fe3O4 samples
showed similar voltage profiles, with well-defined transitions, while
the smallest crystallite-size Fe3O4 resulted in a significantly
smoother discharge curve. Inflection points in the discharge curve
were probed further by constructing a differential capacity analysis
as shown in Fig. 4, where the discharge curve was differentiated
with respect to voltage. One large inflection was evident at 1.65 V.
In addition, a second transition was observed in the region of
1.1–1.3 V, although this transition was less well-defined.
Consistent with the smoother shape of the discharge curve, the
smallest crystallite-size sample showed a much broader peak on
differential-capacity analysis than the two larger crystallite-size
differential capacity (dmAh/dmV)
A
C
2.45 2.05 1.65 1.25 0.85
0.06 voltage (V)
Figure 4. Differential capacity of Li/Fe3O4 batteries as a function of voltage:
共A兲 containing 6.2, 共B兲 8.2, and 共C兲 9.6 nm crystallite-size Fe3O4.
 Electrochemical and Solid-State Letters, 12 共4兲 A91-A94 共2009兲 A93

100
2.0E-06
2 mA/cm2, 1.50 V

current (A)
5 mA/cm2, 1.50 V
1.2E-06
2 mA/cm2, 1.75 V
A
capacity (mAh/g)

5 mA/cm2, 1.75 V
4.0E-07
75 0
-4.0E-07
y = -5.92x + 126.34 2.45 2.25 2.05 1.85 1.65 1.45 1.25 1.05 0.85
2.0E-06
R2 = 0.86 voltage (V)

current (A)
1.2E-06
B
50 y = -5.85x + 110.27 4.0E-07
R2 = 0.85 0
-4.0E-07
2.45 2.25 2.05 1.85 1.65 1.45 1.25 1.05 0.85
y = -7.03x + 111.63 2.0E-06

current (A)
voltage (V)
R2 = 0.95 1.2E-06
25
C
6 7 8 9 10 y = -5.77x + 91.95 4.0E-07
0
R2 = 0.85 -4.0E-07
crystallite size (nm)
2.45 2.25 2.05 1.85 1.65 1.45 1.25 1.05 0.85
voltage (V)
Figure 5. Capacity of Li/Fe3O4 batteries at different voltages 共during pulse
discharge at 2 and 5 mA/cm2兲 as a function of Fe3O4 crystallite size.
Figure 6. CV of Fe3O4 as a function of scan rate: 共A兲 6.00, 共B兲 4.00, and 共C兲
2.00 ⫻ 10−5 V/s.

samples. Delville and co-workers have invoked band theory to con-

ceptualize the smoother voltage profiles of nanocrystalline materials
relative to their well-crystallized homologues.20 Due to their higher
numbers of surface defects 共i.e., distorted coordination polyhedra
and dangling bonds兲, more nanocrystalline materials possess more
sub-bandgap states, effectively decreasing the energy gap between
their conduction and valance bands. During discharge, Li+ insertion
fills these localized sub-bandgap states, allowing an incremental
change in the electrode Fermi energy without any substantial struc-
tural change. Assuming cubic crystallite shape, our Fe3O4 crystallite
sizes of 6.2, 8.2, and 9.6 nm would have corresponding surface area/
volume ratios of 0.96, 0.73, and 0.62, respectively, so the 6.2 nm
sample could be anticipated to have ⬃20% more defects per unit
volume than the 8.2 nm sample, based solely on surface area differ-
ences.
Fe3O4 has mixed iron valence, with 2 FeIII and 1 FeII. Assuming
complete reduction of Fe3+ to Fe2+, the Fe3O4 would transfer two
electrons per formula unit, translating to a 232 mAh/g theoretical
gravimetric capacity. The background voltage data 共collected during
0.08 mA/cm2 discharge兲 was utilized to analyze the overall capacity
of our Fe3O4 batteries. Our Fe3O4 batteries delivered over
230 mAh/g at 1.3 V background, exhibiting good correspondence to
a two electron per formula unit assumption. At 1.5 V background,
our batteries delivered over 110 mAh/g. This shows reasonable cor-
respondence to previous data, where Komaba and co-workers re-
ported a 130 mAh/g capacity to 1.5 V from discharge at room
temperature.13 The small differences in observed capacity are likely
due to differences in cell construction and discharge current utilized
for the tests.
The pulse power capability of the coin cells was evaluated by
applying higher rate 5 s constant current pulses every 2 h. Alternat-
ing current densities of 2 and 5 mA/cm2 were utilized, where these
higher current densities were selected to apply additional demand to
the batteries over a shorter time period. The capacities delivered to
pulse voltages of 1.50 and 1.75 V are shown in Fig. 5. Delivered
capacity increased linearly with decreasing Fe3O4 crystallite size,
where ⬃30% capacity increases were achieved with 6.2 vs 9.6 nm
crystallites. Because the crystallite size effects were different for the
pulse discharge data 共Fig. 5兲 than for the background discharge data
共Fig. 3兲, this suggests that these are kinetically driven phenomena.
The structural changes accompanying lithiation of Fe3O4 have
been investigated by XRD studies2,3,21-24 as well as theoretical en-
ergy simulation studies.25 In the A关B2兴O4 inverse spinel structure, A
cations occupy 1/8 of the tetrahedral sites and B cations occupy 1/2
of the octahedral sites. Magnetite 共Fe3O4兲 is an inverse spinel,
where Fe3+ cations 共A, B⬘兲 occupy tetrahedral and octahedral sites,
while Fe2+ cations occupy other octahedral sites 共B⬙兲. Common
faces between unoccupied octahedral sites and two adjacent tetrahe-
dral sites provide a migration pathway for the A cations. Lithium
ions are mobile in a close-packed anion array with interconnected
edge-sharing octahedra. During lithium insertion, the lithium cations
occupy the vacant octahedral sites and the adjacent tetrahedral Fe3+
ions are displaced into adjacent empty octahedral sites, resulting in a
shift from an inverse spinel to a defect-containing rock salt structure
at x 艋 1. 共1兲 The discharge mechanism at higher values of x is more
complex, where some authors have proposed that extrusion of me-
tallic iron can occur, 共2兲 while others have found no room tempera-
ture extrusion of iron up to x = 2.0.21,22
CV was conducted on Fe3O4 vs lithium counter and reference
electrodes. While there has been extensive collection and discussion
of voltammetry data associated with Fe3O4 and related iron oxides
in acidic aqueous solutions,26-40 to our knowledge, ours is the first
report of slow-scan voltammetry of Fe3O4 in organic electrolyte.
Scan-rate dependence data for a sample of intermediate crystallite
size 共8.2 nm兲 is shown in Fig. 6. The Fe3O4 showed well-resolved
peaks collected at scan rates of 2, 4, and 6 ⫻ 10−5 V/s.
Consistent with the differential capacity data shown in Fig. 4,
one large cathodic peak was present near 1.65 V at all scan rates,
with a second cathodic peak visible at the higher scan rates near
1.10 V. Because the higher potential peak 共⬃1.65 V兲 was visible at
all scan rates, we attribute this peak to Fe3+ reduction within the
solid state. Because one Fe3+ is in an octahedral position while the
other is in a tetrahedral position in Fe3O4, it has been noted that they
should be electrochemically inequivalent, where each ion may be
reduced and solubilized at a different potential;37,41 therefore, it is
possible that reduction of only one type of Fe3+ is represented by
this peak. Thus, we propose that the displacement and reduction of
tetrahedral Fe3+ to octahedral Fe2+ is the most probable assignment
for our 1.65 V cathodic peak. Because the 1.65 and 1.10 V peaks
have similar areas, each should represent a one-electron process,
based on our capacity calculation discussed above. We propose that
reduction of octahedral Fe3+ to octahedral Fe2+ is the most likely
assignment for the 1.10 V peak. For all crystallite sizes, our CV data
were not reversible. This is consistent with the previous statement of
Thackeray and co-workers that lithium-insertion reactions for x
艋 1 in LixFe3O4 were irreversible by CV, although their data were
not reported.4
Conclusion
These results demonstrate the successful use of nanosized Fe3O4
as a lithium-battery cathode material. Crystallite size control of the
Fe3O4 provided the ability to significantly impact its electrochemical

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 A94 Electrochemical and Solid-State Letters, 12 共4兲 A91-A94 共2009兲
properties in primary batteries. On electrochemical test, a strong
correlation between performance and crystallite size was observed,
resulting in a ⬃30% capacity increase across our Fe3O4 crystallite
size range studied. To our knowledge, this is the first study of elec-
trochemical effects of Fe3O4 crystallite size, where all nanocrystal-
line samples were prepared using the same synthetic method. Along
with good battery performance, the environmentally friendly nature
and low cost of this material make it deserving of further electro-
chemical study.
University at Buffalo assisted in meeting the publication costs of this
article.
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