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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- the last few years.5 In fact, in the field of lithium-ion batteries,
top computers and mobile phones. They are also strong contenders carbon materials can be considered to be a mature, well-understood
for use in electric vehicles, because of their high energy density and technology, although there is some debate over the exact lithium
ability to undergo thousands of charge/discharge cycles with mini- insertion mechanisms that occur in some carbon structures. Re-
mal loss of capacity.1 The market for lithium-ion batteries is enor- cently, we have shown that the same electrochemical techniques
mous and growing rapidly. As a result, many researchers around the used to study lithium/carbon interactions can be used to study
world are investigating a wide range of materials for their potential sodium/carbon interactions in hard carbon materials.6 We have now
application as electrode materials in next generation lithium-ion extended our research in this area to quantify the sodium insertion
technology. In keeping with such research, this paper discusses the behavior of a range of carbon materials. From this work, we have
mechanisms for lithium and sodium insertion into carbon electrodes been able to identify the mechanisms through which sodium can be
that can be used to replace lithium metal anodes in lithium-ion bat- incorporated into carbon hosts. By comparing lithium and sodium
teries. insertion behavior, we are also able to provide conclusive evidence
When assessing electrochemical Li behavior, it is useful to mea- to support the mechanisms proposed for lithium insertion into car-
sure the potential difference between the anode material and lithium bon materials by Dahn et al.2
metal as a function of the amount of lithium inserted into the test It has become clear that carbon materials can be separated into
electrode.2 For these experiments, high precision constant current four classes in terms of their behavior in room temperature electro-
sources are used to control the amount of charge flowing through an chemical lithium cells. These classes have been named as2 共i兲 hy-
external circuit between the test and lithium metal electrodes in an drogen containing carbons, 共ii兲 soft carbons exhibiting turbostratic
electrochemical cell. Each electron flowing through the external cir- disorder, 共iii兲 microporous hard carbons, and 共iv兲 graphitic carbons.
cuit corresponds to the movement of one lithium ion from solution Hydrogen-containing carbons exhibit extremely high lithium ca-
into the test electrode during discharge or one lithium ion from the pacities. Much of this capacity occurs along a plateau close to 0 V
test electrode into solution during charge. The quantity of charge with respect to lithium metal during discharge. This inserted lithium
passed is, therefore, a direct measure of the amount of lithium in the
is then removed from the carbon during charge at ⬃1 V with respect
electrode being studied. The lithium content of the test electrode is
to the metal. This hysteresis in the electrochemical profile has been
generally converted to specific capacity, the amount of charge
attributed to the high activation energy present during the rehybrid-
共mAh兲 passed per gram of active material. The potential difference
ization of hydrogen terminated aromatic carbon centers to aliphatic
between the metal and the test electrodes can then be plotted against
centers, through formation of compounds analogous to organo-
the lithium capacity. This potential difference between the two elec-
trodes provides a direct measure of the chemical potential of lithium lithium species (-C2H2Li2-兲.7
in the test electrode relative to the 共constant兲 chemical potential of Soft carbons heated to intermediate temperatures 共1000-2000°C兲
the metal itself. Thus, such plots provide detailed information on the are believed to contain small crystallite domains of roughly 10-12
chemical environment of the sites accessible to lithium within the graphene layers stacked approximately parallel to each other. The
material under investigation. layers are randomly rotated and shifted relative to each other, pro-
When these electrochemical measurements are completed in ducing turbostratic disorder.8 As this disorder creates interlayer
cells containing beryllium windows, X-ray scattering measurements lithium insertion sites with a range of chemical environments, the
can also be completed on the working electrodes. These in situ capacity develops over a range of potentials, giving a ‘‘sloping volt-
X-ray studies provide a powerful means for identifying the struc- age’’ electrochemical profile.
tural changes occurring as lithium ions move into and out of the test Hard carbon materials can contain significant quantities of
electrode.3 Thus, a combination of electrochemical and in situ X-ray nanoscale porosity, which can be modeled by a series of graphene
measurements can be used to identify the mechanisms through sheets arranged much like a house of cards. Some of the ‘‘cards’’
which lithium is electrochemically incorporated into a candidate may comprise two or three stacked layers, and hence, there is scope
electrode material. for some interlayer insertion to occur in a similar manner to the soft
Current lithium-ion batteries use carbon materials for the anode.4 carbons. Thus, the electrochemical curves display a sloping voltage
Thus, the electrochemical interactions between lithium and carbon region. In addition to this interlayer capacity, these carbons can also
materials have been studied extensively by a number of authors over 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
* Electrochemical Society Student Member.
this low voltage plateau.10,11 Recently, we presented in situ small
** Electrochemical Society Active Member. angle X-ray scattering results showing that capacity along the low
z
E-mail: jeff.dahn@dal.ca 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 thick were pressed at 15,000 kPa from 0.1 g of this powder.
would occur for lithium insertion along the low voltage plateau. For in situ wide-angle X-ray scattering 共WAXS兲 cells, a 17 mm
It is generally accepted that lithium interacts with graphite during diam hole was cut into the stainless steel can of the coin cell. A
electrochemical studies to form intercalation compounds,13 where 0.010 in. thick beryllium window was glued over this hole with
intercalation can be defined as the reversible insertion of guest at- Roscobond pressure-sensitive adhesive 共Rosco, Port Chester, NY兲.
oms into the host structure with minimal structural rearrangement. The can and pellet were then taken into the glove box for assembly.
During this intercalation process, the lithium forms a set of staged The pellet was centered on the beryllium window. Enough electro-
compounds, where a stage n structure contains n graphitic layers lyte solution was added to saturate the pellet before two Celgard
between each lithium layer. The development of the different stages separators were added. The lithium or sodium metal counter elec-
are essentially phase transitions that produce a set of plateaus in the trodes were then added, followed by a spacer and spring and the cell
potential vs. capacity curves. These plateaus all occur at potentials was crimped shut. After the cell was removed from the glove box,
close to that of lithium metal itself, which is one of the main reasons torr-seal 共Varian兲 epoxy resin was used to seal the external joint
why graphitic carbons have been so successful as anode materials in between the cell rim and the beryllium. These cells were discharged
rechargeable lithium-ion batteries. at 750/500 ␮A 共Li/Na兲 until a potential difference of 0.2 V was
In this paper, we present results to show the way in which so- reached. The current was then reduced to 500/300 ␮A 共Li/Na兲. Once
dium interacts with the four different classes of carbon and compare metal plating was observed through the appearance of a sharp peak
this behavior with lithium behavior in the same carbons. In addition, at ⬃35° 共lithium兲 and 29° 共sodium兲, the current direction was re-
through the use of in situ X-ray scattering studies, we present con- versed, and the cells were charged until the potential of the carbon
clusive evidence to support the proposed mechanisms. electrode was 2 V relative to the metal.
For the in situ small angle X-ray scattering 共SAXS兲 measure-
Experimental 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
Hydrogen-containing carbon was prepared by heating polyvinyl process was similar to that used for the WAXS cells, although no
chloride 共Aldrich Chemical Company Inc.兲 to 600°C under flowing spacer or spring was included. These cells were discharged and
argon 共UHP-Praxair兲 in a Lindberg tube furnace. Soft carbon was charged under the same conditions as were used for the in situ
prepared by taking Crowley pitch 共Crowley Tar Company Ltd.兲 and WAXS cells. The position of the plating point was inferred from the
heating it to 1000°C in the same furnace under the same conditions. electrochemical profile.
Microporous hardcarbon was prepared by heating dehydrated glu- X-ray scattering measurements were completed with a Siemens
cose 共Aldrich Chemical Company Inc.兲 to 1000°C in flowing argon. D5000 diffractometer equipped with a copper tube and a graphite
A sample of Fluka graphite was used with no further heat-treatment monochromator. For the WAXS cells, the divergence slit was set at
for the graphitic carbon. The carbons were all crushed to ⬍75 ␮m 0.6° and the receiving slit was set at 0.6 mm. The intensity was
prior to use. Both thin film and pellet-type electrodes were then recorded for scattering angles between 15 and 60° at 0.1° incre-
prepared from these powders. ments with a count time of 30 s at each angle. The lower cutoff
Thin film electrodes were prepared by coating a slurry of the angle was selected to minimize attenuation of the beam by the edges
carbon powder onto copper foil with a doctor blade. The slurry was of the cell can. For the SAXS cells, the divergence slit was set at
prepared by mixing carbon powder with 5 wt % carbon black 共Super 0.1° while the receiving slit was set at 0.1 mm. The intensity was
S-MMM Carbon兲 and 10 wt % of a solution containing 10 wt % recorded at 0.05° increments 共30 s count time at each angle兲 over
polyvinylidene fluoride binder dissolved in N-methyl pyrrolidinone the angular range of 0.3 to 15° scattering angle. For both the WAXS
共NMP兲. Additional NMP was added to achieve the desired consis- and SAXS cells, the X-ray scans were repeated many times in order
tency. The carbon black was added to improve electrical contact to obtain scattering profiles for a complete discharge/charge cycle of
between particles. The electrode foils were dried in an oven at each cell.
100°C to remove the NMP. Circular electrodes containing ⬃8 mg of Gas adsorption measurements were completed on the samples
carbon were punched from the foils for electrochemical coin cell using a Micromeritics Autoscan 2010 gas adsorption porosimeter
fabrication. The electrodes were taken into an argon filled glove box with nitrogen gas as the adsorbate. After degassing at 250°C under
and placed on the can. A small amount of electrolyte solution 共1 M vacuum, the sample tube was transferred to the analysis station and
MPF6, M ⫽ Li or Na, dissolved in 33:67 vol % mixture of ethylene then allowed to equilibrate with sequential 10 cm3/g doses of N2
carbonate and diethyl carbonate兲 was added followed by a Celgard 共UHP-Liquide Air兲. Equilibration was deemed to have occurred
polypropylene separator. Two polypropylene mesh separators and when the rate of change of gas pressure was less than 0.01%, aver-
another Celgard separator were also added to the sodium cells. A foil aged over ten 20 s intervals. The gas adsorption data is presented as
of the appropriate metal was added, followed by a steel spacer and volume adsorbed as a function of relative pressure, P/ P 0 , where P 0
spring. The cells were then hermetically sealed prior to being re- is the saturation pressure of the gas 共101 kPa for N2 at 77 K兲.
moved from the glove box, and were installed on separate channels
of a Moli 共E-One Moli Energy Ltd.兲 constant current charge/ Results and Discussion
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 During the first discharge process in the electrochemical test
(⬃66 ␮A/cm2兲, while the sodium cells were run at 40 ␮A cells, some of the lithium or sodium reacts at the surface of the
carbon electrode with electrolyte species to form an electronically
(⬃33 ␮A/cm2兲. Shortly after electroplating of metal on the elec-
insulating but ionically conductive surface layer known as the solid
trode surface was observed 共as indicated by a reduced gradient dur-
electrolyte interphase 共SEI兲.14 This SEI formation is one of the pri-
ing discharge below 0 V with respect to the metal兲, the current
mary contributors to irreversible capacity 共essentially the amount of
direction was reversed and the cells were charged to a trip point of
charge lost between the first discharge and subsequent charge
2 V with respect to the metal. This discharge/charge cycle was then
cycles兲 for carbon electrodes. The reactions occur somewhere be-
repeated.
tween 0.2 and 1 V with respect to the metal, with the potential and
Pellet-type electrodes for in situ studies were prepared by mixing
capacity dependent on the carbon. This dependence is probably re-
the carbon powder with 5 wt % carbon black and a solution of
lated to different surface chemistries of the different carbons. As this
ethylene propylene diene terpolymer 共EPDM兲 dissolved in cyclo-
paper is intended to discuss the mechanisms for reversible sodium
hexane 共Caledon Laboratories Ltd.兲. The resultant slurry was mixed
and lithium insertion into carbon materials, changes in irreversible
in a shaker bottle with zirconia media beads, and then the cyclohex-
capacity between the different carbons are not discussed.
ane was allowed to evaporate in a fume hood, leaving a powder
containing approximately 2.5% EPDM binder. Pellets ⬃0.7 mm Graphitic carbons.—The voltage vs. capacity curve for the gra-

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Journal of The Electrochemical Society, 148 共8兲 A803-A811 共2001兲 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
Figure 1. Electrochemical profiles for 共a兲 lithium and 共b兲 sodium insertion occurs because the attractive interaction between intercalated Na
into Fluka graphite. 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.

phitic carbon against lithium 共Fig. 1a兲 is typical for such carbons, a Hydrogen-containing carbon.—Figure 2 presents capacity vs.
potential curves for the hydrogen-containing carbon. Panel 2a pre-
reversible capacity equivalent to ⬃1 lithium for every 6 carbons
sents the lithium data and panel 2b presents sodium performance of
occurring along a set of plateaus in the potential curve. These pla-
the same carbon. Panels 2c and d present the differential capacity
teaus correspond to the development of staged intercalation com-
curves derived from these potential curves. The lithium capacity is
pounds, where the nth stage implies that n carbon layers separate 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 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- Figure 3. Insertion of lithium and sodium into soft carbon. Panels 共a兲 and
sertion are shown in panels 共b兲 and 共d兲. 共c兲 show lithium behavior. Panels 共b兲 and 共d兲 show sodium behavior.

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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 A807

Figure 8. Selected in situ X-ray scattering scans for sodium insertion into Figure 9. 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- nanoporous hard carbon. The first scan has been included as the dashed line
quent scans for reference. The approximate location of each scan along the on subsequent scans for reference. The approximate location of each scan
potential vs. capacity profile for the cell is shown in panel f 共top right兲. along the potential vs. capacity profile for the cell is indicated on the top
right panel.

reduced capacity. The corresponding peak during the discharge oc-


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

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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 A809

Figure 13. Selected in situ SAXS scans for sodium insertion into soft car- 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- 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 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. 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 vs. scattering angle 共represented by q, the X-ray scattering vector兲
carbon, the drop in intensity observed for the sodium was greater as shown in Fig. 12. In this figure, the larger nanopore contribution
than that seen for lithium, consistent with destructive interference for the hard carbon appears as a broad hump in Fig. 12b. SAXS
occurring to a greater extent for the species with the higher X-ray curves for these carbons can be modeled well by Eq. 1, which is an
scattering cross section. extension of the model equation derived by Kalliat et al.23
As the potentials for lithium and sodium insertion and removal
along the low voltage plateau are close to that of the metal itself, A Ba 61 共 ⌬␳ 兲 2 Ca 62
there is very little charge transfer from the carbon to the alkali 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
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 In this equation, A is a refineable parameter for the sloping back-
study to show differences in porosity. It can be seen that the hard ground, B and C are proportional to the number of pores of average
carbon can accommodate much larger volumes of N2 at very low correlation lengths a 1 and a 2 , respectively, D is a constant back-
relative pressures. This type I isotherm is typical for a material con- ground parameter, ⌬␳ is the electron density contrast between the
taining a large volume of nanopores.22 The hysteresis between the nanopores, and the carbon matrix and the magnitude of the scatter-
adsorption and desorption branches of the isotherm implies that the ing vector is
carbon contains restricted pore openings. The soft carbon produced
4␲ sin ␪
a type II isotherm, typical of materials containing negligible nano- q⫽
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 This model fits experimental data well, as shown in Fig. 12b 共hard
共that had no low voltage plateau兲 had no open nanoporosity. carbon兲 and d 共soft carbon兲. The relative contributions of each of the
As shown recently, in situ SAXS studies are a powerful tool for parameters to the fits 共indicated by the refineable variables兲 are
studying electron density changes in nanopores in carbon shown in Fig. 12a 共hard carbon兲 and c 共soft carbon兲. The increased
electrodes.12 In that paper, it was shown that the pores in nanopo- nanopore contribution in the hard carbon requires a much larger
rous hard carbon were filled with sodium only along the low voltage contribution from the B term.
plateau. This work has now been extended to include lithium inser- Sample scans from the in situ SAXS run for sodium insertion
tion into hard carbon and sodium insertion into soft carbon. into the soft carbon are shown in Fig. 13. The fit to the first scan in
The electron density fluctuations of nanopores embedded in a panel a has been included in subsequent panels as a dashed line for
matrix generate significant intensity at small angles. This intensity is reference. Even though this figure only includes data for the dis-
superimposed on a sloping background in a log-log plot of intensity charge 共as the cell shorted out during charge兲, it can be seen that

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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.

Figure 16. Fit parameters obtained for SAXS scans of lithium insertion into
soft carbon. The calculated electron density contrast assuming that pore fill-
there is very little, or no, change in the SAXS pattern over the ing occurs only along the low voltage plateau is shown as a dashed line on
nanopore range. We attribute the increase in intensity at low q to the panel c.
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 constant along the sloping voltage region, decreases during dis-
voltage plateau during charge 共panel c to d兲 showing that this was a charge along the low voltage plateau then increases during charge
reversible effect. The same behavior was also seen for the sodium along the low voltage plateau. The magnitude of the changes ob-
cell 共Fig. 15兲. If the electron density between the pores and the served for both the lithium and sodium cells agree well with those
carbon matrix decreases 共as would happen if lithium or sodium in- calculated from a simple nanopore filling model 共included as a
serts into the pores兲, the contribution from the B term would drop, dashed line in Fig. 16c and 17c兲. This gives further confidence that
leading to a reduction of intensity at intermediate q values. As so- both sodium and lithium insert into nanopores along the low voltage
dium has a higher scattering cross section than lithium, the magni- plateau and that this process is reversible.
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 Conclusions
voltage plateau during discharge is much more pronounced for the From the data presented here, it is apparent that there are a num-
sodium cell than for the lithium cell. For the sodium cell, the inten- ber of similarities between lithium and sodium insertion mecha-
sity at low q increased as current flowed through the cell. As with nisms in carbon materials with the exception of graphitic carbons.
the soft carbon cell, this behavior may have resulted from the de- Graphitic carbons can accommodate large amounts of lithium
velopment of microcracks in the electrode particles caused by ex- through a staging process, where the lithium ions insert between the
pansion of the carbon matrix. graphite layers. It appears that such sites are unavailable to sodium
This SAXS data clearly shows that the electron density contrast at normal pressures because the chemical potential of sodium in
within the nanopores decreases during alkali insertion and increases such sites would be lower than the chemical potential of the metal
during alkali removal along the low voltage plateau. This can be itself. As a result, it is more energetically favorable for the metal to
quantified using Eq. 1 by fitting the first scan well and then only electroplate on the surface of the carbon.
allowing the electron density contrast, ⌬␳ and C 共to allow for the In hydrogen-containing carbons, in addition to an interlayer in-
development of microcracks兲 terms to vary for subsequent scans. sertion process, both lithium and sodium bind to hydrogen termi-
The quality of the fit can be determined by calculating a ␹ 2 value for nated carbon centers, forcing the carbons to rehybridize. This rehy-
each scan. More details on this procedure can be found in our pre- bridization is an activated process, resulting in hysteresis in the
vious paper.12 The results obtained for the SAXS cells are presented potential curves. The magnitude of the hysteresis is significantly
in Fig. 16 共lithium兲 and 17 共sodium兲. It can be seen that, for both the lower for sodium insertion, possibly because the extent of rehybrid-
lithium and sodium cells, the fitted electron density contrast remains ization required is much lower.

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