Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲 A803

0013-4651/2001/148共8兲/A803/9/$7.00 © The Electrochemical Society, Inc.

The Mechanisms of Lithium and Sodium Insertion in Carbon

Materials
D. A. Stevensa,* and J. R. Dahnb,**, z
a
Department of Chemistry, bDepartments of Physics and Chemistry, Dalhousie University, Halifax,
Nova Scotia, Canada

In this paper, we compare the interactions of lithium and sodium with a range of carbon materials in electrochemical cells.
Through wide angle in situ X-ray scattering studies, we demonstrate that both lithium and sodium can be inserted into the
interlayer space in disordered carbon materials. This insertion process is accompanied by an increase in the interlayer spacing in
these materials. Small-angle in situ scattering studies are presented to clearly show the insertion of lithium and sodium into
nanopores within disordered hard carbons. We also show that very little, if any, sodium can be inserted into graphitic materials in
contrast to the large capacity seen for lithium insertion.
© 2001 The Electrochemical Society. 关DOI: 10.1149/1.1379565兴 All rights reserved.

Manuscript received September 8, 2000. Available electronically June 25, 2001.

Rechargeable lithium-ion batteries are widely used to power lap-
top computers and mobile phones. They are also strong contenders
for use in electric vehicles, because of their high energy density and
ability to undergo thousands of charge/discharge cycles with mini-
mal loss of capacity.1 The market for lithium-ion batteries is enor-
mous and growing rapidly. As a result, many researchers around the
world are investigating a wide range of materials for their potential
application as electrode materials in next generation lithium-ion
technology. In keeping with such research, this paper discusses the
mechanisms for lithium and sodium insertion into carbon electrodes
that can be used to replace lithium metal anodes in lithium-ion bat-
teries.
When assessing electrochemical Li behavior, it is useful to mea-
sure the potential difference between the anode material and lithium
metal as a function of the amount of lithium inserted into the test
electrode.2 For these experiments, high precision constant current
sources are used to control the amount of charge flowing through an
external circuit between the test and lithium metal electrodes in an
electrochemical cell. Each electron flowing through the external cir-
cuit corresponds to the movement of one lithium ion from solution
into the test electrode during discharge or one lithium ion from the
test electrode into solution during charge. The quantity of charge
passed is, therefore, a direct measure of the amount of lithium in the
electrode being studied. The lithium content of the test electrode is
generally converted to specific capacity, the amount of charge
共mAh兲 passed per gram of active material. The potential difference
between the metal and the test electrodes can then be plotted against
the lithium capacity. This potential difference between the two elec-
trodes provides a direct measure of the chemical potential of lithium
in the test electrode relative to the 共constant兲 chemical potential of
the metal itself. Thus, such plots provide detailed information on the
chemical environment of the sites accessible to lithium within the
material under investigation.
When these electrochemical measurements are completed in
cells containing beryllium windows, X-ray scattering measurements
can also be completed on the working electrodes. These in situ
X-ray studies provide a powerful means for identifying the struc-
tural changes occurring as lithium ions move into and out of the test
electrode.3 Thus, a combination of electrochemical and in situ X-ray
measurements can be used to identify the mechanisms through
which lithium is electrochemically incorporated into a candidate
electrode material.
Current lithium-ion batteries use carbon materials for the anode.4
Thus, the electrochemical interactions between lithium and carbon
materials have been studied extensively by a number of authors over
* Electrochemical Society Student Member.
** Electrochemical Society Active Member.
z
E-mail: jeff.dahn@dal.ca
the last few years.5 In fact, in the field of lithium-ion batteries,
carbon materials can be considered to be a mature, well-understood
technology, although there is some debate over the exact lithium
insertion mechanisms that occur in some carbon structures. Re-
cently, we have shown that the same electrochemical techniques
used to study lithium/carbon interactions can be used to study
sodium/carbon interactions in hard carbon materials.6 We have now
extended our research in this area to quantify the sodium insertion
behavior of a range of carbon materials. From this work, we have
been able to identify the mechanisms through which sodium can be
incorporated into carbon hosts. By comparing lithium and sodium
insertion behavior, we are also able to provide conclusive evidence
to support the mechanisms proposed for lithium insertion into car-
bon materials by Dahn et al.2
It has become clear that carbon materials can be separated into
four classes in terms of their behavior in room temperature electro-
chemical lithium cells. These classes have been named as2 共i兲 hy-
drogen containing carbons, 共ii兲 soft carbons exhibiting turbostratic
disorder, 共iii兲 microporous hard carbons, and 共iv兲 graphitic carbons.
Hydrogen-containing carbons exhibit extremely high lithium ca-
pacities. Much of this capacity occurs along a plateau close to 0 V
with respect to lithium metal during discharge. This inserted lithium
is then removed from the carbon during charge at ⬃1 V with respect
to the metal. This hysteresis in the electrochemical profile has been
attributed to the high activation energy present during the rehybrid-
ization of hydrogen terminated aromatic carbon centers to aliphatic
centers, through formation of compounds analogous to organo-
lithium species (-C2H2Li2-兲.7
Soft carbons heated to intermediate temperatures 共1000-2000°C兲
are believed to contain small crystallite domains of roughly 10-12
graphene layers stacked approximately parallel to each other. The
layers are randomly rotated and shifted relative to each other, pro-
ducing turbostratic disorder.8 As this disorder creates interlayer
lithium insertion sites with a range of chemical environments, the
capacity develops over a range of potentials, giving a ‘‘sloping volt-
age’’ electrochemical profile.
Hard carbon materials can contain significant quantities of
nanoscale porosity, which can be modeled by a series of graphene
sheets arranged much like a house of cards. Some of the ‘‘cards’’
may comprise two or three stacked layers, and hence, there is scope
for some interlayer insertion to occur in a similar manner to the soft
carbons. Thus, the electrochemical curves display a sloping voltage
region. In addition to this interlayer capacity, these carbons can also
exhibit extensive capacity at a potential close to that of the metal
itself along the low voltage plateau.9 A number of theories have
been presented to explain the nature of the insertion process along
this low voltage plateau.10,11 Recently, we presented in situ small
angle X-ray scattering results showing that capacity along the low
voltage plateau results from the insertion of sodium into nanopores

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A804 Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲
in the carbon.12 We suggested that, by analogy, a similar process
would occur for lithium insertion along the low voltage plateau.
It is generally accepted that lithium interacts with graphite during
electrochemical studies to form intercalation compounds,13 where
intercalation can be defined as the reversible insertion of guest at-
oms into the host structure with minimal structural rearrangement.
During this intercalation process, the lithium forms a set of staged
compounds, where a stage n structure contains n graphitic layers
between each lithium layer. The development of the different stages
are essentially phase transitions that produce a set of plateaus in the
potential vs. capacity curves. These plateaus all occur at potentials
close to that of lithium metal itself, which is one of the main reasons
why graphitic carbons have been so successful as anode materials in
rechargeable lithium-ion batteries.
In this paper, we present results to show the way in which so-
dium interacts with the four different classes of carbon and compare
this behavior with lithium behavior in the same carbons. In addition,
through the use of in situ X-ray scattering studies, we present con-
clusive evidence to support the proposed mechanisms.
Experimental
Hydrogen-containing carbon was prepared by heating polyvinyl
chloride 共Aldrich Chemical Company Inc.兲 to 600°C under flowing
argon 共UHP-Praxair兲 in a Lindberg tube furnace. Soft carbon was
prepared by taking Crowley pitch 共Crowley Tar Company Ltd.兲 and
heating it to 1000°C in the same furnace under the same conditions.
Microporous hardcarbon was prepared by heating dehydrated glu-
cose 共Aldrich Chemical Company Inc.兲 to 1000°C in flowing argon.
A sample of Fluka graphite was used with no further heat-treatment
for the graphitic carbon. The carbons were all crushed to ⬍75 ␮m
prior to use. Both thin film and pellet-type electrodes were then
prepared from these powders.
Thin film electrodes were prepared by coating a slurry of the
carbon powder onto copper foil with a doctor blade. The slurry was
prepared by mixing carbon powder with 5 wt % carbon black 共Super
S-MMM Carbon兲 and 10 wt % of a solution containing 10 wt %
polyvinylidene fluoride binder dissolved in N-methyl pyrrolidinone
共NMP兲. Additional NMP was added to achieve the desired consis-
tency. The carbon black was added to improve electrical contact
between particles. The electrode foils were dried in an oven at
100°C to remove the NMP. Circular electrodes containing ⬃8 mg of
carbon were punched from the foils for electrochemical coin cell
fabrication. The electrodes were taken into an argon filled glove box
and placed on the can. A small amount of electrolyte solution 共1 M
MPF6, M ⫽ Li or Na, dissolved in 33:67 vol % mixture of ethylene
carbonate and diethyl carbonate兲 was added followed by a Celgard
polypropylene separator. Two polypropylene mesh separators and
another Celgard separator were also added to the sodium cells. A foil
of the appropriate metal was added, followed by a steel spacer and
spring. The cells were then hermetically sealed prior to being re-
moved from the glove box, and were installed on separate channels
of a Moli 共E-One Moli Energy Ltd.兲 constant current charge/
discharge unit. As the diffusion rates for lithium are higher than for
sodium, the lithium cells were run at a constant current of 80 ␮A
(⬃66 ␮A/cm2兲, while the sodium cells were run at 40 ␮A
(⬃33 ␮A/cm2兲. Shortly after electroplating of metal on the elec-
trode surface was observed 共as indicated by a reduced gradient dur-
ing discharge below 0 V with respect to the metal兲, the current
direction was reversed and the cells were charged to a trip point of
2 V with respect to the metal. This discharge/charge cycle was then
repeated.
Pellet-type electrodes for in situ studies were prepared by mixing
the carbon powder with 5 wt % carbon black and a solution of
ethylene propylene diene terpolymer 共EPDM兲 dissolved in cyclo-
hexane 共Caledon Laboratories Ltd.兲. The resultant slurry was mixed
in a shaker bottle with zirconia media beads, and then the cyclohex-
ane was allowed to evaporate in a fume hood, leaving a powder
containing approximately 2.5% EPDM binder. Pellets ⬃0.7 mm
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thick were pressed at 15,000 kPa from 0.1 g of this powder.
For in situ wide-angle X-ray scattering 共WAXS兲 cells, a 17 mm
diam hole was cut into the stainless steel can of the coin cell. A
0.010 in. thick beryllium window was glued over this hole with
Roscobond pressure-sensitive adhesive 共Rosco, Port Chester, NY兲.
The can and pellet were then taken into the glove box for assembly.
The pellet was centered on the beryllium window. Enough electro-
lyte solution was added to saturate the pellet before two Celgard
separators were added. The lithium or sodium metal counter elec-
trodes were then added, followed by a spacer and spring and the cell
was crimped shut. After the cell was removed from the glove box,
torr-seal 共Varian兲 epoxy resin was used to seal the external joint
between the cell rim and the beryllium. These cells were discharged
at 750/500 ␮A 共Li/Na兲 until a potential difference of 0.2 V was
reached. The current was then reduced to 500/300 ␮A 共Li/Na兲. Once
metal plating was observed through the appearance of a sharp peak
at ⬃35° 共lithium兲 and 29° 共sodium兲, the current direction was re-
versed, and the cells were charged until the potential of the carbon
electrode was 2 V relative to the metal.
For the in situ small angle X-ray scattering 共SAXS兲 measure-
ments, an additional Be window was added to the top of the cell,
sealed in a similar manner to the window in the can. The assembly
process was similar to that used for the WAXS cells, although no
spacer or spring was included. These cells were discharged and
charged under the same conditions as were used for the in situ
WAXS cells. The position of the plating point was inferred from the
electrochemical profile.
X-ray scattering measurements were completed with a Siemens
D5000 diffractometer equipped with a copper tube and a graphite
monochromator. For the WAXS cells, the divergence slit was set at
0.6° and the receiving slit was set at 0.6 mm. The intensity was
recorded for scattering angles between 15 and 60° at 0.1° incre-
ments with a count time of 30 s at each angle. The lower cutoff
angle was selected to minimize attenuation of the beam by the edges
of the cell can. For the SAXS cells, the divergence slit was set at
0.1° while the receiving slit was set at 0.1 mm. The intensity was
recorded at 0.05° increments 共30 s count time at each angle兲 over
the angular range of 0.3 to 15° scattering angle. For both the WAXS
and SAXS cells, the X-ray scans were repeated many times in order
to obtain scattering profiles for a complete discharge/charge cycle of
each cell.
Gas adsorption measurements were completed on the samples
using a Micromeritics Autoscan 2010 gas adsorption porosimeter
with nitrogen gas as the adsorbate. After degassing at 250°C under
vacuum, the sample tube was transferred to the analysis station and
then allowed to equilibrate with sequential 10 cm3/g doses of N2
共UHP-Liquide Air兲. Equilibration was deemed to have occurred
when the rate of change of gas pressure was less than 0.01%, aver-
aged over ten 20 s intervals. The gas adsorption data is presented as
volume adsorbed as a function of relative pressure, P/ P 0 , where P 0
is the saturation pressure of the gas 共101 kPa for N2 at 77 K兲.
Results and Discussion
During the first discharge process in the electrochemical test
cells, some of the lithium or sodium reacts at the surface of the
carbon electrode with electrolyte species to form an electronically
insulating but ionically conductive surface layer known as the solid
electrolyte interphase 共SEI兲.14 This SEI formation is one of the pri-
mary contributors to irreversible capacity 共essentially the amount of
charge lost between the first discharge and subsequent charge
cycles兲 for carbon electrodes. The reactions occur somewhere be-
tween 0.2 and 1 V with respect to the metal, with the potential and
capacity dependent on the carbon. This dependence is probably re-
lated to different surface chemistries of the different carbons. As this
paper is intended to discuss the mechanisms for reversible sodium
and lithium insertion into carbon materials, changes in irreversible
capacity between the different carbons are not discussed.
Graphitic carbons.—The voltage vs. capacity curve for the gra-
 Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲
Figure 1. Electrochemical profiles for 共a兲 lithium and 共b兲 sodium insertion
into Fluka graphite.
phitic carbon against lithium 共Fig. 1a兲 is typical for such carbons, a
reversible capacity equivalent to ⬃1 lithium for every 6 carbons
occurring along a set of plateaus in the potential curve. These pla-
teaus correspond to the development of staged intercalation com-
pounds, where the nth stage implies that n carbon layers separate
Figure 2. Electrochemical profiles for alkali insertion into hydrogen con-
taining carbon. Panels 共a兲 and 共c兲 show lithium insertion capacity and differ-
ential capacity behavior, respectively. The equivalent graphs for sodium in-
sertion are shown in panels 共b兲 and 共d兲.
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A805
each layer of lithium atoms. As the capacity increases, the lithium
layers need to be closer together and hence, the stage number de-
creases.
In contrast to the lithium cell, the potential/capacity curve of
graphite against sodium 共Fig. 1b兲 shows that very little sodium can
be incorporated into the carbon host. In fact, much of the capacity
observed corresponds to a combination of plating and stripping of
sodium from the electrode surface and reversible insertion of so-
dium into the carbon black in the electrode. The onset of plating can
be seen in the inset and has been marked by a vertical line on the
figure. As the carbon black content of the electrodes made in this
study was low, its contribution to reversible capacity can be ignored
for most materials without introducing significant error. For ex-
ample, in these electrodes, the small amount of super S contributes
⬃9 mAh/g to the lithium capacity15 and ⬃5 mAh/g to the sodium
capacity 共our measurement兲. In this case, because the sodium capac-
ity is so low, the contribution from the carbon black cannot be ig-
nored. After correcting for these external contributions, the amount
of sodium that can be reversibly inserted into this graphite, is ex-
tremely small 共equivalent to the development of ⬃NaC186兲.
The observation that very little sodium intercalates into graphitic
carbon under normal pressures is consistent with observations from
other authors.16,17 Theoretical calculations suggest that this behavior
occurs because the attractive interaction between intercalated Na
species and the carbon layers is extremely weak.18 Thus there is no
strong energetic driving force to encourage the sodium to intercalate
rather than deposit as metal on the electrode surface.
Hydrogen-containing carbon.—Figure 2 presents capacity vs.
potential curves for the hydrogen-containing carbon. Panel 2a pre-
sents the lithium data and panel 2b presents sodium performance of
the same carbon. Panels 2c and d present the differential capacity
curves derived from these potential curves. The lithium capacity is
extremely high in these materials 共equivalent to the formation of
⬃Li5C6兲 during the initial cycles. However, this capacity has been
seen to fade rapidly with subsequent cycles.19 The other important
Figure 3. Insertion of lithium and sodium into soft carbon. Panels 共a兲 and
共c兲 show lithium behavior. Panels 共b兲 and 共d兲 show sodium behavior.
A806 Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲

Figure 4. In situ X-ray scattering scans for lithium insertion into soft car-
bon. Each scan has been offset from the last by 20 counts/s for clarity.

feature of the lithium curve is that much of the lithium is removed

during charge at a potential significantly higher than the insertion
potential. As stated in the introduction, this hysteresis in the voltage
profile has been attributed to the presence of residual hydrogen ter-
minating aromatic fragments in the carbon matrix. These carbon
centers provide sites for lithium insertion provided they can rehy-
bridize to form direct C-Li bonds. This bond formation has a large
activation barrier and hence the lithium can only bond to these sites Figure 6. Insertion of lithium and sodium into hard carbon. Panels 共a兲 and
共c兲 show lithium behavior. Panels 共b兲 and 共d兲 show sodium behavior.
when the potential shifts to lower voltages 共higher energy兲. This
activation barrier also causes the potential for removal of lithium
from these sites to shift to higher voltages.20 The hysteresis results
from a combination of these two effects.
A comparison of Fig. 2a with 2b shows that the sodium capacity
of this carbon is significantly lower than its lithium capacity. This
reduction in capacity when moving from lithium to sodium is a
common trait for many of the carbon materials we have tested,
although it is much more pronounced in the hydrogen containing
carbons than in other materials, primarily because of the extremely
high lithium capacities of these materials. The sodium profile also
exhibits hysteresis between discharge and charge although the mag-
nitude of the hysteresis is significantly lower than that seen for the
lithium cell. This is more obvious in the differential capacity curves,
where the broad peak centered around 0.9 V on charge 共lithium兲
occurs around 0.5 V for sodium and is also much smaller, implying

Figure 7. Selected in situ X-ray scattering scans for lithium insertion into
soft carbon. The first scan has been included as the dashed line on subse-
Figure 5. In situ X-ray scattering scans for sodium insertion into soft car- quent scans for reference. The approximate location of each scan along the
bon. Each scan has been offset from the last by 20 counts/s for clarity. potential vs. capacity profile for the cell is shown in panel f 共top right兲.

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 Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲
Figure 8. Selected in situ X-ray scattering scans for sodium insertion into
soft carbon. The first scan has been included as the dashed line on subse-
quent scans for reference. The approximate location of each scan along the
potential vs. capacity profile for the cell is shown in panel f 共top right兲.
reduced capacity. The corresponding peak during the discharge oc-
curs at close to 0 V for lithium and is difficult to resolve from
surface electroplating. In the sodium curve, the peak occurs during
discharge at around 0.3 V. Thus the magnitude of the hysteresis
decreases from ⬃0.9 V for lithium to only ⬃0.2 V for sodium.
Soft carbon.—The similarities between sodium and lithium in-
sertion mechanisms become more apparent in the soft carbon
sample. The potential curves shown in Fig. 3a 共lithium兲 and b 共so-
dium兲 both show the same trend: a sloping region that extends from
1 to ⬃0 V. Again, as was seen for the hydrogen containing carbon,
the sodium capacity is lower than the lithium capacity. In such ma-
terials, the random layer distribution inherent in these turbostrati-
cally disordered carbons creates a distribution of sites into which
lithium or sodium ions can be inserted. As the measured potential is
related to the chemical potential of the lithium or sodium in the
carbon relative to the metal, then the distribution of sites generates a
distribution of chemical potentials, and hence, a range of insertion
potentials. This, in turn, generates a sloping potential curve. We
believe therefore that the sloping region of the potential profile cor-
responds to insertion of sodium or lithium between turbostratically
arranged layers. The reduced capacity of the sodium cells implies
that less sodium can be inserted into a given site, or alternatively,
that many of the sites available for lithium insertion are unavailable
to sodium, possibly for reasons similar to those proposed for the
graphitic carbon.
In order to investigate the insertion mechanism共s兲 for the soft
carbon further, we performed in situ WAXS studies of both lithium
and sodium insertion. Figure 4 shows the resultant set of X-ray
patterns obtained for the lithium cell and Fig. 5 shows the scans
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A807
Figure 9. Selected in situ X-ray scattering scans for lithium insertion into
nanoporous hard carbon. The first scan has been included as the dashed line
on subsequent scans for reference. The approximate location of each scan
along the potential vs. capacity profile for the cell is indicated on the top
right panel.
recorded on the sodium cell. No corrections have been made to this
data, apart from adding a constant offset to each scan in order to
make the trends easier to observe.
It can be seen that for both metals, as the cell discharged along
the sloping region of the potential profile, the broad peak around 25°
共we identify this as the 002 peak, consistent with the 002 interlayer
spacing peak that is observed for graphite兲 shifted to lower angles
and its intensity decreased. Both the magnitude of the peak shift and
the decrease in peak intensity were larger for the sodium cell than
for the lithium cell. When the cells were switched to charge, the 002
peak shifted back toward the original angle and its peak intensity
increased, although it did not return completely to its original posi-
tion.
In order to more clearly show the intensity changes, Fig. 7 and 8
present selected scans from the in situ WAXS runs. The scan for the
cell before current flow was started is included with each scan as a
reference.
We believe this data clearly shows that both lithium and sodium
insert between turbostratically disordered graphene layers, when dis-
charging along the sloping voltage profile. The shift in peak position
to lower angles implies that the layers are forced apart as interlayer
insertion occurs. The drop in intensity is consistent with the pres-
ence of scattering species between the layers. Interlayer species will
scatter X-rays out of phase with those from the layers themselves
over the angular range of the 002 peak and hence, destructive inter-
ference will occur. As sodium has a higher scattering cross section
than lithium, the amplitude of the scattered waves from the sodium
species would be expected to be higher than that from lithium spe-
cies in the same location. Thus, the extent of destructive interference
A808 Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲

Figure 11. N2 gas adsorption profiles for soft 共lower curve兲 and hard 共upper
curve兲 carbon samples used in this study.

disordered, the X-ray intensities are low. This makes resolving in-
tensity changes and peak shifts difficult. Selected scans from the in
situ runs presented in Fig. 9 共lithium兲 and 10 共sodium兲 do show a
drop in intensity of the 002 peak upon lithium or sodium insertion
along the sloping potential portion of the curve during discharge,

Figure 10. Selected in situ X-ray scattering scans for sodium insertion into
nanoporous hard carbon. The first scan has been included as the dashed line
on subsequent scans for reference. The approximate location of each scan
along the potential vs. capacity profile for the cell is indicated on the top
right panel.

would be expected to be higher with sodium than lithium, leading to

a greater drop in intensity. This is consistent with the experimental
patterns presented above.
Hard carbon.—Figure 6a and c present the electrochemical
lithium profile for the hard carbon material prepared for this study.
The equivalent sodium profiles are shown in Fig. 6b and d. It can be
seen that these electrochemical profiles can be divided into two re-
gions, a sloping voltage region extending down to ⬃0.2 V, and a
high capacity plateau at low potential 共the low voltage plateau兲. It
appears from the lithium data that a small amount of capacity can be
attributed to interactions with residual hydrogen, in a manner similar
to that seen for the hydrogen containing carbon. This is most clearly
shown in the differential capacity curve, where there is a small
hump at around 1 V with respect to the metal. The equivalent peak
around 0.4 V for sodium cannot be resolved from the sloping volt-
age capacity. This is not surprising because the magnitude of the
peak for the lithium cell is small, implying only a small amount of
capacity. It has already been shown that the capacity that can be
derived from interactions with hydrogen terminated carbon centers
is significantly lower for sodium cells.
As with the soft carbon, hard carbons contain some parallel
stacking of carbon layers, although X-ray diffraction measurements
show that the stacks generally contain only single, double, or triple
layers.21 Thus, in these materials there are sites into which interlayer
insertion can occur. We believe therefore that the sloping potential
region in the hard carbon corresponds to interlayer insertion of
lithium and/or sodium, in a manner similar to such insertion into the Figure 12. Sample SAXS curves for hard 共a and b兲 and soft 共c and d兲
soft carbon. Again to verify this hypothesis, we completed in situ carbons. The contributions of each of the fit parameters to the overall fit 共the
X-ray diffraction studies. Because hard carbons tend to be highly smooth lines in panels b and d兲 are shown in panels a and c.

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 Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲
Figure 13. Selected in situ SAXS scans for sodium insertion into soft car-
bon. The fit to the first scan has been included as the dashed line on subse-
quent scans for reference. The approximate location of each scan along the
potential vs. capacity profile for the cell is indicated on the top right panel.
followed by an increase in intensity during charge. As with the soft
carbon, the drop in intensity observed for the sodium was greater
than that seen for lithium, consistent with destructive interference
occurring to a greater extent for the species with the higher X-ray
scattering cross section.
As the potentials for lithium and sodium insertion and removal
along the low voltage plateau are close to that of the metal itself,
there is very little charge transfer from the carbon to the alkali
species. This would occur if the sodium and lithium inserted into
nanopores in the carbon. Figure 11, therefore, presents nitrogen gas
adsorption isotherms for the hard and soft carbons prepared in this
study to show differences in porosity. It can be seen that the hard
carbon can accommodate much larger volumes of N2 at very low
relative pressures. This type I isotherm is typical for a material con-
taining a large volume of nanopores.22 The hysteresis between the
adsorption and desorption branches of the isotherm implies that the
carbon contains restricted pore openings. The soft carbon produced
a type II isotherm, typical of materials containing negligible nano-
scale porosity. The gas adsorption data, therefore, shows that the
hard carbon 共that produced a low voltage plateau兲 contains nanopo-
rosity that could accommodate alkali species while the soft carbon
共that had no low voltage plateau兲 had no open nanoporosity.
As shown recently, in situ SAXS studies are a powerful tool for
studying electron density changes in nanopores in carbon
electrodes.12 In that paper, it was shown that the pores in nanopo-
rous hard carbon were filled with sodium only along the low voltage
plateau. This work has now been extended to include lithium inser-
tion into hard carbon and sodium insertion into soft carbon.
The electron density fluctuations of nanopores embedded in a
matrix generate significant intensity at small angles. This intensity is
superimposed on a sloping background in a log-log plot of intensity
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A809
Figure 14. Selected in situ SAXS scans for lithium insertion into hard car-
bon. The fit to the first scan has been included as the dashed line on subse-
quent scans for reference. The approximate location of each scan along the
potential vs. capacity profile for the cell is indicated on the top right panel.
vs. scattering angle 共represented by q, the X-ray scattering vector兲
as shown in Fig. 12. In this figure, the larger nanopore contribution
for the hard carbon appears as a broad hump in Fig. 12b. SAXS
curves for these carbons can be modeled well by Eq. 1, which is an
extension of the model equation derived by Kalliat et al.23
A Ba 61 共 ⌬␳ 兲 2 Ca 62
I共 q 兲 ⫽ 3.3 ⫹ 2 2 2 ⫹ ⫹D 关1兴
q 共 1 ⫹ a 1q 兲 共 1 ⫹ a 22 q 2 兲 2
In this equation, A is a refineable parameter for the sloping back-
ground, B and C are proportional to the number of pores of average
correlation lengths a 1 and a 2 , respectively, D is a constant back-
ground parameter, ⌬␳ is the electron density contrast between the
nanopores, and the carbon matrix and the magnitude of the scatter-
ing vector is
4␲ sin ␪
q⫽
␭
This model fits experimental data well, as shown in Fig. 12b 共hard
carbon兲 and d 共soft carbon兲. The relative contributions of each of the
parameters to the fits 共indicated by the refineable variables兲 are
shown in Fig. 12a 共hard carbon兲 and c 共soft carbon兲. The increased
nanopore contribution in the hard carbon requires a much larger
contribution from the B term.
Sample scans from the in situ SAXS run for sodium insertion
into the soft carbon are shown in Fig. 13. The fit to the first scan in
panel a has been included in subsequent panels as a dashed line for
reference. Even though this figure only includes data for the dis-
charge 共as the cell shorted out during charge兲, it can be seen that
A810 Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲
Figure 15. Selected in situ SAXS scans for sodium insertion into hard car-
bon. The fit to the first scan has been included as the dashed line on subse-
quent scans for reference.
there is very little, or no, change in the SAXS pattern over the
nanopore range. We attribute the increase in intensity at low q to the
development of microcracks in the carbon matrix.
The set of scans for lithium insertion into the hard carbon 共Fig.
14兲 show a drop in intensity at intermediate q values along the low
voltage plateau 共panel b to c兲. The intensity returned along the low
voltage plateau during charge 共panel c to d兲 showing that this was a
reversible effect. The same behavior was also seen for the sodium
cell 共Fig. 15兲. If the electron density between the pores and the
carbon matrix decreases 共as would happen if lithium or sodium in-
serts into the pores兲, the contribution from the B term would drop,
leading to a reduction of intensity at intermediate q values. As so-
dium has a higher scattering cross section than lithium, the magni-
tude of this effect would be larger for the sodium cell. It can be seen
in Fig. 15 that this is the case; the drop in intensity along the low
voltage plateau during discharge is much more pronounced for the
sodium cell than for the lithium cell. For the sodium cell, the inten-
sity at low q increased as current flowed through the cell. As with
the soft carbon cell, this behavior may have resulted from the de-
velopment of microcracks in the electrode particles caused by ex-
pansion of the carbon matrix.
This SAXS data clearly shows that the electron density contrast
within the nanopores decreases during alkali insertion and increases
during alkali removal along the low voltage plateau. This can be
quantified using Eq. 1 by fitting the first scan well and then only
allowing the electron density contrast, ⌬␳ and C 共to allow for the
development of microcracks兲 terms to vary for subsequent scans.
The quality of the fit can be determined by calculating a ␹ 2 value for
each scan. More details on this procedure can be found in our pre-
vious paper.12 The results obtained for the SAXS cells are presented
in Fig. 16 共lithium兲 and 17 共sodium兲. It can be seen that, for both the
lithium and sodium cells, the fitted electron density contrast remains
Downloaded 09 Jul 2012 to 128.148.252.35. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp
Figure 16. Fit parameters obtained for SAXS scans of lithium insertion into
soft carbon. The calculated electron density contrast assuming that pore fill-
ing occurs only along the low voltage plateau is shown as a dashed line on
panel c.
constant along the sloping voltage region, decreases during dis-
charge along the low voltage plateau then increases during charge
along the low voltage plateau. The magnitude of the changes ob-
served for both the lithium and sodium cells agree well with those
calculated from a simple nanopore filling model 共included as a
dashed line in Fig. 16c and 17c兲. This gives further confidence that
both sodium and lithium insert into nanopores along the low voltage
plateau and that this process is reversible.
Conclusions
From the data presented here, it is apparent that there are a num-
ber of similarities between lithium and sodium insertion mecha-
nisms in carbon materials with the exception of graphitic carbons.
Graphitic carbons can accommodate large amounts of lithium
through a staging process, where the lithium ions insert between the
graphite layers. It appears that such sites are unavailable to sodium
at normal pressures because the chemical potential of sodium in
such sites would be lower than the chemical potential of the metal
itself. As a result, it is more energetically favorable for the metal to
electroplate on the surface of the carbon.
In hydrogen-containing carbons, in addition to an interlayer in-
sertion process, both lithium and sodium bind to hydrogen termi-
nated carbon centers, forcing the carbons to rehybridize. This rehy-
bridization is an activated process, resulting in hysteresis in the
potential curves. The magnitude of the hysteresis is significantly
lower for sodium insertion, possibly because the extent of rehybrid-
ization required is much lower.
 Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲
Figure 17. Fit parameters obtained for SAXS scans of sodium insertion into
soft carbon. The calculated electron density contrast assuming that pore fill-
ing occurs only along the low voltage plateau is shown as a dashed line on
panel c.
In turbostratically disordered soft carbon structures, both lithium
and sodium insert between graphene layers, resulting in some ex-
pansion of the interlayer spacing. In these materials, the turbostratic
disorder produces sites with a distribution of chemical environ-
ments, which results in a sloping voltage profile during discharge
and charge.
Downloaded 09 Jul 2012 to 128.148.252.35. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp
A811
In nanoporous hard carbons, in addition to insertion between
approximately parallel graphene sheets, both lithium and sodium
can fill the pores in the structure in a process analogous to adsorp-
tion. The low voltage plateau in these materials corresponds to such
a process, with the implication that the chemical potential of the
lithium/sodium species in these pores is close to that of the metal
itself.
Although for all these materials, the sodium capacity is clearly
lower than the equivalent lithium capacity, the amount of sodium
that can be inserted into some carbon materials is potentially large
enough to allow for the development of rechargeable sodium-ion
batteries. In addition, the electrochemical profiles of these materials
exhibit significant capacity at a potential close to that of sodium
metal. Thus the voltage penalty incurred by using such carbons in a
real sodium-ion cell in place of sodium metal would be small.
Acknowledgments
D.S. would like to acknowledge financial support form Comalco
Aluminum Ltd. 共Australia兲. J.D. acknowledges the support of
NSERC and 3M Corporation.
Dalhousie University assisted in meeting the publication costs of this
article.
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