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Beaulieu Et Al. - 2001 - A System For Performing Simultaneous in Situ Atomic Force Microscopy Optical Microscopy Measurements On Electrode Materials For Lithium-Ion Batteries
Beaulieu Et Al. - 2001 - A System For Performing Simultaneous in Situ Atomic Force Microscopy Optical Microscopy Measurements On Electrode Materials For Lithium-Ion Batteries
a兲
Author to whom correspondence should be addressed; electronic mail:
jeff.dahn@dal.ca FIG. 1. The AFM inside the glovebox prior to closing the box.
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3314 Rev. Sci. Instrum., Vol. 72, No. 8, August 2001 Beaulieu et al.
FIG. 3. 共a兲 Photograph of the wet cell used in our studies. 共b兲 Top view and
共c兲 side view schematic representation of the wet cell used in our studies.
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Rev. Sci. Instrum., Vol. 72, No. 8, August 2001 AFM/optical microscopy on Li-ion batteries 3315
FIG. 6. 共a兲 Schematic representation of the rough sample 共dark gray兲 on a III. EXPERIMENTAL SETUP
flat substrate 共hashed area兲. 共b兲 Effect on the roughness when the sample
共dark gray兲 on a flat substrate 共hash area兲 is doubled in sized. 共c兲 The Figure 1 shows the glovebox, with the purifier system to
maximum peak to valley distance and 共d兲 average roughness of the electrode
surface obtained from a statistical analysis of the AFM images collected the left, in which all experiments were conducted. The glove-
during the experiment highlighted in Fig. 5. box is connected to the dry-train by two 38 mm diameter
共inner diameter兲 pipes which allow the circulation of Ar from
in situ atomic force microscopy 共AFM兲/optical microscopy the glovebox to the purifier. The interior of the glovebox is
system suited to these and other electrochemical studies. divided in 2. The right side of the glovebox, not shown in
In situ AFM and scanning tunneling microscopy have Fig. 1, is used for sample preparation while the left side of
been used to study electrodeposition12,13 and nickel hydrox- the glovebox is used to hold the AFM. The AFM sits on two
ide electrodes.14,15 In particular, in situ AFM, has been used granite slabs weighing 11 kg 共small slab兲 and 70 kg 共large
to study the formation of the solid electrolyte interphase on slab兲 each. The large granite slab is suspended from the ceil-
model surfaces like highly oriented pyrolytic graphite.16 Re- ing of the glovebox by a combination of two flexible rubber
cently a system has been constructed to perform in situ stud- cords and one metal spring at each corner. The metal springs
ies on electrochemical cells.17,18 This system, although inge- are used to support the large mass while the rubber cords are
nious in its design, is very restrictive due to its small size. In used as vibration dampers.
this article we show how a scanning probe microscope Figure 2 shows a schematic representation of the AFM
共SPM兲 system can be incorporated into a full size double setup inside the glovebox. The AFM sits centrally on the
glovebox and used to study air sensitive materials. The ad- small granite slab that sits on rubber dampers that sit on the
vantages of using a large glovebox are numerous. Commer- large granite slab. Because of the sensitivity of the AFM a
cial gloveboxes equipped with purification systems allow for draft shield was designed and constructed to allow for the
an inert atmosphere to be maintained for long periods of continual circulation of argon gas inside the glovebox by the
time. A full size glovebox allows the user a much better purification system. The draft shield rests on dampers that
control of his/her equipment. Moreover, sample preparation rest on the large granite slab. An environmental chamber
and sample imaging are done in the same environment with- below the AFM 共also shown in Fig. 2兲 further isolates the
out any risk of contamination due to relocation. sample. The CCD camera, represented by the black square, is
used to optically monitor the topography of our samples to
obtain information on the micron scale.
II. EQUIPMENT
Figure 3共a兲 shows a picture of the wet cell used in our
A Molecular Imaging 共Pheonix, Arizona兲 PicoScan SPM experiments. This picture shows the position of the sample as
with two AFM scanners 共37⫻37 m and 6⫻6 m兲 was well as the lithium foil used as both the reference and
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3316 Rev. Sci. Instrum., Vol. 72, No. 8, August 2001 Beaulieu et al.
counter electrode. Figures 3共b兲 and 3共c兲 show schematic charge 共or charge兲 to which the AFM images 关Figs. 5共a兲–
views of the construction of the wet cell. The sample sits on 5共f兲兴 correspond. A scale bar at the lower left indicates the
a copper current collector and is held in place by a rare earth time corresponding to 1 Li/metal and the scale bar at the
magnet under the baseplate. The current collector is electri- lower right indicates the capacity scale in mAh/g. Note that
cally isolated from the baseplate by a thin glass plate. This 1900 mAh/g corresponds to 4.4 Li atoms per metal atom for
ensures that the AFM and the Keithley 236, used to control this film. Figures 5共a兲–5共d兲 show the evolution of the mor-
the cell, are electrically isolated. The Li metal electrode sits phology of the film as it reacts with lithium during the first
on a ledge in the polypropylene well and is cold welded onto discharge. The charge cycle 共removing lithium兲 of this ex-
four nickel spikes which protrude through the walls of the periment shows different results than those obtained for the
well. Wires from the copper current collector and the nickel discharge cycle due to poor adhesion between the metallic
spikes are fed to a female plug at the front of the wet cell. All film and the substrate. This is seen by the loss of the AFM
electrical connections from the inside of the glovebox to the image as shown in Fig. 5共f兲 midway during the first charge
outside are made by a commercial airtight electrical cycle. The poor adhesion of this film can be seen more
feedthrough 共not shown兲.
clearly from the optical images taken simultaneously.
Figures 5共a兲–5共d兲 suggest that the insertion of lithium
IV. EXPERIMENTAL RESULTS into the metal film during the first discharge causes virtually
Figure 4 shows an AFM image19 of the surface of a no change to the surface morphology. However, the vertical
Si–Sn11 metallic film studied in our experiments. Figure 4共a兲 distance corresponding to maximum contrast 共white to black兲
shows the two-dimensional AFM image of a 12⫻12 m por- increases from 共a兲 to 共d兲 showing a proportional increase in
tion of the electrode surface. The color scheme from black to corrugation with film thickness. The top panels of Fig. 6
white corresponds to 0–100 nm as shown by the scale bar on show a sketch of an initially rough film, on a flat substrate,
the right. Figure 4共b兲 shows a three-dimensional representa- that then doubles in thickness everywhere 共much like the
tion of the same portion of the surface. As can more clearly thickness change of an electrode material after incorporation
be seen, the surface is corrugated on the nanometer scale. of lithium兲. Notice that the corrugation also doubles which
Figure 5 shows the results of an in situ AFM implies that the thickness change suffered by the electrode
experiment20 conducted on the electrode shown in Fig. 4. can be obtained from the change in roughness.21 The in-
The cell voltage is plotted versus time 共bottom abscissa兲 and crease in corrugation of the electrode surface is best de-
AFM scan number 共top abscissa兲 in Fig. 5共g兲. The indicated scribed by comparing the change in the average roughness
points on the voltage curve show the points during the dis- 共mean absolute deviation from the average film height兲 with
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Rev. Sci. Instrum., Vol. 72, No. 8, August 2001 AFM/optical microscopy on Li-ion batteries 3317
lithium content. The lower panels of Fig. 6 show the average posited has a roughness itself that is negligible compared to
roughness and the maximum peak to valley distance versus that of the roughness of the film on the substrate. The aver-
lithium content for images collected during the experiment age roughness of our polished stainless steel substrates is
described by Fig. 5. Both the maximum peak to valley dis- about 80 Å 共average of measurements over three substrates兲,
tance and the average roughness increase, as expected, with only a factor of 2 smaller than that of the sputtered film.
the insertion of lithium into the electrode. Furthermore, we did not measure the roughness of the sur-
It is not possible to make quantitative measurements of face after the deposition of the 4-m-thick copper layer.
the volume expansion of the film based on roughness Since the alloy film is deposited on an initially rough surface,
changes alone, unless the substrate on which the film is de- the original roughness of the alloy film has a contribution
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3318 Rev. Sci. Instrum., Vol. 72, No. 8, August 2001 Beaulieu et al.
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Rev. Sci. Instrum., Vol. 72, No. 8, August 2001 AFM/optical microscopy on Li-ion batteries 3319
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