Microscopy and Microanalysis (2020), 1–11

doi:10.1017/S1431927620024368

Original Article

Ultra-Microtome for the Preparation of TEM Specimens from Battery

Cathodes
Hanlei Zhang1,2,3, Chongmin Wang4 and Guangwen Zhou2,3*
1
Engineering Research Center of Nano-Geomaterials of Ministry of Education, Faculty of Materials Science and Chemistry, China University of Geosciences, No. 68
Jincheng Street, East Lake High-Tech Development Zone, Wuhan 430078, Hubei, P. R. China; 2Materials Science and Engineering Program & Department of
Mechanical Engineering, State University of New York, Binghamton, NY 13902, USA; 3NorthEast Center for Chemical Energy Storage, State University of New York,
Binghamton, NY 13902, USA and 4Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352, USA

Abstract
With the wide application of ultra-microtome sectioning in the preparation of transmission electron microscopy (TEM) specimens with
bio- and organic materials, here, we report an ultra-microtome-based method for the preparation of TEM specimens from cathodes of
Li-ion batteries. The ultra-microtome sectioning reduces the sample thickness to tens of nanometers and yields atomic resolution from
the core region of particles of hundreds of nanometers. Analysis indicates that the mechanical cross-sectioning introduces no observable
microstructural artifacts or structural damage, such as microcracking and nanoporosity. These results demonstrate the high efficiency of
the ultra-microtome approach in preparing well-thinned specimens of particulate materials that allow for atomic-scale TEM imaging of
a large number of sectioned particles in one single TEM specimen, thereby providing statistically significant results of the TEM analysis.
Key words: transmission electron microscopy, sample preparation, artifact, atomic resolution, ultra-microtome
(Received 2 April 2020; revised 28 June 2020; accepted 7 July 2020)

Introduction most materials with enough fragility (Mori et al., 1999), but it
does not work with soft materials. Also, it can significantly change
Specimen preparation is a critical step in the transmission elec-
the macroscale morphology of materials, as well as introducing
tron microscopy (TEM) analysis of materials (Klepeis et al.,
undesirable artifacts such as microcracking and porosity (Ahn
1987; Ishitani & Yaguchi, 1996; Sun et al., 2005; Mayer et al.,
& Peacor, 1986). FIB is relatively expensive and time-consuming
2007). Well-prepared specimens reveal the authentic microstruc-
in preparing TEM specimens. FIB works well with a large number
tural features of materials by minimizing misleading artifacts gen-
of materials and usually does not change the materials’ macro-
erated by the specimen preparation process (Dai et al., 2001). To
scale morphology, but it can possibly change the atomic-scale
perform TEM imaging with clear atomic resolution, a well-shaped
morphology via ion implantation and knock-on effects (Lezec
thin-film specimen with a thickness of <100 nm is usually desired
et al., 1991; Volkert & Minor, 2007). These two effects can be
(Burghardt & Droleskey, 2006; Zhao et al., 2017). Unfortunately,
minimized via the state-of-the-art cryo-FIB technique which
most of the raw materials for observation are randomly shaped
involves freezing the specimens with liquid nitrogen while sec-
with a much larger thickness. To overcome this universal issue,
tioning (Wang et al., 2012; Zhang et al., 2016), which has demon-
multiple thinning methods have been developed for obtaining
strated to minimize the ion-beam damage to sensitive materials
TEM specimens with a desirable thickness, including mechanical
such as biomaterials (Schertel et al., 2013; Schaffer et al., 2019)
cutting and ion-beam milling (Barna et al., 1999; McCaffrey et al.,
and battery cathodes (Zachman et al., 2018, 2020). FIB can
2001; Liu et al., 2007), crushing and grinding (Zhang & Howes,
easily prepare TEM specimens as large as 10 μm (Li et al.,
1994; Zhang et al., 2011), and focused ion beam (FIB) cutting
2006; Bashir et al., 2019), meeting most requirements in specimen
(Giannuzzi & Stevie, 1999; Schaffer et al., 2012; Lu et al., 2013).
preparation. However, when analyzing particulate materials of
All these methods have different advantages and disadvantages,
hundreds of nanometers (such as the cathode particles we study
meaning that they need to be carefully chosen based on the spe-
in this work), even the largest FIB sample can only contain a
cific characterization requirements. Mechanical cutting and mill-
dozen of particles, considering their dispersion. Such a sample
ing are suitable for large, bulk materials with enough ductility
volume is not sufficient for obtaining statistically significant
(Puttick et al., 1994), while they do not work with powder or
results.
very fragile materials. Crushing and grinding can be useful for
Particulate materials ranging from nanometers to hundreds of
micrometers are widely used in many fields of the industry such
as energy storage (Yoshida et al., 2013; Siu et al., 2018; Zhang
*Author for correspondence: Guangwen Zhou, E-mail: gzhou@binghamton.edu
et al., 2018), catalysis (He et al., 2017; Stamenkovic et al., 2017),
Cite this article: Zhang H, Wang C, Zhou G (2020) Ultra-Microtome for the
Preparation of TEM Specimens from Battery Cathodes. Microsc Microanal. and structural composites (Flom & Arsenault, 1989; Kumlutaş
doi:10.1017/S1431927620024368 et al., 2003; Yang et al., 2003). Accordingly, there is an increasing
© Microscopy Society of America 2020

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 2 H. Zhang et al.
requirement to characterize their microstructures and properties
with TEM techniques. Among the TEM specimen preparation
methods mentioned above, only FIB is suitable for the prepara-
tion of high-quality TEM specimens from particles. The other
methods either fail in working with particles or generate undesir-
able artifacts. Although FIB has the ability to locate and section
target particles with a high precision, it is also very time-
consuming and only analyzes a relatively small area at one time,
as discussed above. Therefore, FIB is not suitable for analyzing
a large number of particles of hundreds of nanometers to obtain
statistically significant information.
To overcome these drawbacks, we have used a TEM specimen
preparation method with the ultra-microtome technique, a
mechanical sectioning method that produces millimeter-sized
slices in lateral with a thickness of only tens of nanometers, allow-
ing for the analysis of tens of thousands of particles in one TEM
specimen. The ultra-microtome method was originally developed
for sectioning biomaterials and organic materials (Reymond &
Pickett-Heaps, 1983; Harris et al., 2006; Graf et al., 2009;
Schrand et al., 2010; Brown et al., 2014), which is feasible based
on the fact that these materials are soft enough and can be cut
smoothly with the diamond knife in microtomy. Following the
pioneering work by Malis & Steele (1990) and Mcmahon &
Malis (1995), ultra-microtomy has been seen increasingly as an
attractive alternative means of producing TEM specimens of
hard and inorganic materials (Becker & Bange, 1993;
Antonovsky, 1995; Glanvill, 1995; Quintana, 1997). A main chal-
lenge for ultra-microtomy is that the diamond knife sectioning
may generate mechanical defects in the specimen such as cracking
and porosity, as schematically shown in Figures 1a and 1b.
Another challenge of the ultra-microtomy method resides in the
cutting of robust inorganic nanoparticles (NP) such as silicates
and metal oxides (Tucker et al., 1985; Mori et al., 1992;
Hochella et al., 1999). The NPs are embedded within a matrix
Fig. 1. Challenges in the ultra-microtome sectioning of inorganic materials. (a,b) Schematics showing the cracks and porosity generated by ultra-microtome cut-
ting. (c) Schematic showing the ultra-microtome sectioning of NPs imbedded in the epoxy. (d) Schematic showing the poor connection between the NPs and the
matrix material upon the ultra-microtome cutting.
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material (e.g., epoxy) and then sliced into thin films, as schemati-
cally shown in Figure 1c. During this process, the diamond knife
can push the NPs out of the matrix (Fig. 1d) instead cutting
through them (Fig. 1c), failing in thinning the NPs. This phenom-
enon is observed with multiple popular nanomaterials such as
zeolite (Haswell et al., 2003), silicates (Messenger et al., 2003),
and metal oxides (Tucker et al., 1985). In these materials, the
internal chemical bonding within the NP is stronger than its con-
nection with the epoxy matrix, so the interfacial connection pref-
erably disassembles upon the microtome cutting.
In this work, we developed an ultra-microtome-based method
for the preparation of TEM specimens from lithium transition
metal oxides (battery cathode particles). Cathode materials are
widely synthesized by a precipitation process involving primary
particles and secondary particles (May et al., 2018; Zhang et al.,
2018; Boesenberg et al., 2019). Primary particles normally have
a size in the hundred nanometer range, and secondary particles
usually have a particle size in the micrometer scale. We show
the feasibility of preparing cathode particles into well-thinned
specimens that allow for atomic-scale TEM imaging of hundreds
of thousands of sectioned particles in one single TEM specimen,
thereby providing a statistically significant result of the TEM anal-
ysis. The results also show that the ultra-microtome sectioning
process does not introduce observable mechanical damage or
microstructural artifacts into the specimens. This ultra-
microtome method may find broader applicability in sectioning
other particulate materials for TEM observations.
Experimental
Materials
In this work, we use the industrial-level LiNi0.80Co0.15Al0.05O2
(NCA) cathode material for Li-ion batteries as the example to
 Microscopy and Microanalysis 3

Fig. 2. Preparation of TEM specimens with ultra-microtome cutting. (a) Bar-shaped capsule models for the preparation of epoxy bars containing cathode particles.
(b) Solidified epoxy bar containing cathode materials in its head, as marked with an orange arrow. (c) Schematic showing the slicing of the epoxy bar with ultra-
microtome. (d) Scanning electron microscopy (SEM) image of the pristine NCA secondary particles. (e) Schematic showing the NCA material used for ultra-
microtome cutting, which is secondary particles composed of primary particles of hundreds of nanometers. (f) TEM analysis of the specimen prepared with
ultra-microtome.

demonstrate the capability of the ultra-microtome method in pre-
paring TEM specimens. The large size of the primary particles in
the NCA cathode (hundreds of nanometers) prohibits direct
microscopic observation of the core area. Therefore, there is a sig-
nificant lack of information regarding the microstructural feature
in the bulk for such large potato-like cathode particles, mainly
due to the challenge in preparing appropriate specimens for
TEM analysis (Zhang et al., 2017b, 2017c). Pristine NCA cathode
material was obtained from TODA America Inc. X-ray diffraction
analysis in our previous work (Zhang et al., 2017b) indicated that
the pristine material has an ideal R
3m crystal configuration. The
pristine NCA material was prepared into battery cathodes by mix-
ing the active material, carbon black, and polyvinylidene fluoride
(PVDF) with a weight ratio of 8:1:1, using N-methyl-2-pyrroli-
done solvent. Cathodes with 3–5 mg of active NCA were assem-
bled in 2325-type coin cells in a glovebox filled with helium.
The electrolyte was 1 M LiPF6 dissolved in a mixture of ethylene
carbonate (EC) and dimethyl carbonate (DMC), with a volume
ratio of 1:1. The coin cells were cycled with an MPG2 multichan-
nel potentiostat (Biologic). Galvanostatic cycling was performed
at a rate of C/10 with a current density of 15 mA/g, between
3.0 and 4.3 V.
Ultra-Microtome Cutting for the Preparation of TEM Specimens
The TEM specimen preparation was performed using a
Reichert-Jung Ultracut E ultra-microtome machine, equipped
with a 45° diamond knife manufactured by DiATOME U.S.
Pristine materials and cycled cathodes scraped from the current
collector were mixed with white resin (Electron Microscopy
Sciences, hard grade), pulled into a bar-shaped capsule model
with a pointed head (Fig. 2a) and settled at 60°C for 24 h for sol-
idification. Cathode particles, especially cycled samples, tend to
undergo degradation in air. Therefore, the influence of air expo-
sure and heating on cycled samples could be a concern for the
ultra-microtome method and preventive measures need to be
taken to minimize such an effect. For instance, air exposure can
be minimized by rapidly sealing the cathode particles with
epoxy when preparing the epoxy bars for ultra-microtome. Our
results indicate that brief air exposure (a few seconds) and the
subsequent curing of the solidified epoxy resin at 60°C for 24 h
do not induce noticeable changes to the morphology and atomic
structure of pristine and cycled NCA particles. This is confirmed
by comparing the cycled samples sectioned by ultra-microtome
and FIB. As demonstrated in our previous work (Zhang et al.,
2017c), primary particles sectioned by ultra-microtome and FIB
yield the similar feature of (003) intragranular cracking and the
presence of a rock-salt layer between the crack. This negligible
effect is further confirmed by examining the thickness of the sur-
face rock-salt layer formed on the 30-cycle NCA sample. Our
TEM imaging shows that the thickness of the rock-salt layer on
the microtome-sectioned particles is similar to that on uncut par-
ticles (Zhang et al., 2017b), indicating that the sample preparation
with ultra-microtome does not induce noticeable growth of the
rock-salt layer. Solidified resin bars containing the objective mate-
rials were extracted from the capsule model and trimmed with a
razor blade (Fig. 2b) for ultra-microtome sectioning. Since only
the head of the resin bar is used in the microtome cutting, the
material of interest is purposely concentrated in the head region
to increase the particle concentration in the TEM specimen.
Slices with a nominated thickness of ∼50 nm were sectioned
from the tip of the resin bars using the ultra-microtome machine

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 4 H. Zhang et al.
at a cutting rate of ∼0.8 mm/s, as schematically shown in
Figure 2c. More details regarding the sample-cutting procedures
with ultra-microtome can be found in the literature (Hughes
et al., 2014; Sun et al., 2017).
Figure 2d presents an SEM image of pristine NCA particles,
indicating that the pristine material is composed secondary parti-
cles of 5–10 μm, which consist of primary particles of ∼300–
1000 nm. Since the atomic HRTEM imaging usually requires a
specimen thickness of less than ∼100 nm (Buseck et al., 1989;
Williams & Carter, 2009), only the surface region along the
thin edges of the primary particles is suitable for HRTEM imag-
ing, while no atomic resolution can be obtained from the core
area (Zhang et al., 2017a). The thinning process of the NCA par-
ticles via ultra-microtome is schematically summarized in Figures
2e and 2f. Before cutting (Fig. 2e), the material is secondary par-
ticles of micrometers, composed of primary particles of hundreds
of nanometers. Besides the large thickness, the overlapping of the
primary particles also prevents atomic resolution. After cutting
(Fig. 2f), the secondary particle is sectioned into a slice with a
thickness of ∼50 nm. The internal structures of the particles are
well maintained, as will be demonstrated later. The boundaries
between neighboring primary particles are not cracked, and no
microstructural defects are introduced into the crystal lattice.
This overcomes the overly high thickness and overlapping of pri-
mary particles, making the slice a well-defined subject for TEM
observations, as schematically illustrated in Figure 2f.
TEM Observation
TEM and high-resolution TEM (HRTEM) observations were per-
formed using an FEI Titan 80-300 microscope with a field emis-
sion gun (FEG) and an image aberration corrector, operated at an
acceleration voltage of 300 kV. Scanning TEM (STEM) high-angle
angular dark-field (HAADF) observation was performed using an
FEI Titan 80-300 microscope with an FEG and a probe aberration
corrector, operated at an acceleration voltage of 300 kV.
SEM Observation
SEM observation was performed in the second electron mode
using a Hitachi S-4800 FE-SEM, operated at an acceleration volt-
age of 2 kV.
TEM Simulation
HRTEM simulations in this work were performed using the JEMS
TEM simulation software. The microscopic parameters used for
the simulation were from the Titian 80-300 microscope, the
same as the microscope used for the experiment in this work.
Figure 5e is obtained with the established crystal structure of
LiNi0.80Co0.15Al0.05O2 (Mori et al., 2009), a sample thickness of
23 nm and a defocus of 41 nm.
Results and Discussion
Morphology of the TEM Specimen Prepared with
Ultra-Microtome
The epoxy slices prepared with ultra-microtome were placed on
copper grids coated with a lacey carbon film for TEM imaging,
as shown in the SEM image in Figure 3a (pristine NCA). The
lacey provides a steady support for the epoxy slice, avoiding
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sample drifting or vibration under the electron beam irradiation.
Zoom-in view from inside the epoxy slice (Figs. 3b, 3c) clearly
shows the presence of cathode particles embedded in the epoxy
for TEM imaging. The epoxy film in Figures 3b and 3c is almost
invisible at the high magnification, demonstrating its ultra-thin
thickness.
Atomic-Resolution Imaging Enabled with Ultra-Microtome
Figure 4a presents a zoom-out TEM image of a pristine NCA par-
ticle sectioned with ultra-microtome. The particle has a relative
uniform contrast without significantly enhanced darkness in the
core region, indicating that the thickness of the entire particle
has been uniformly reduced. Meanwhile, TEM imaging of the
sliced particle shows an intact morphology without any observ-
able cracking or fractured feature, indicating the absence of
mechanical damage from the ultra-microtome process. Figures
4b to 4e present HRTEM views obtained progressively from the
particle surface toward the core region (0–280 nm), which show
that atomic imaging is eligible across the particle, indicating
that the thickness of whole particle is reduced under ∼100 nm.
It is worth mentioning that the most comment zone axis for
observing the layered phase is along the [010] direction to reveal
the layered feature, as shown in Figures 5a and 5b and previous
studies (Lin et al., 2014a, 2014b; Yan et al., 2017). Since the inter-
layer d-spacing is very large (∼4.7 Å), the interlayer feature can be
resolved for relatively lower-resolution images, as shown in
Figure 5c. Here, we purposely avoided the commonly used
[010] zone axis and selected the [2
21] zone axis because the latter
can be used to better demonstrate the good quality of the
microtome-sectioned sample to clearly resolve the narrower lat-
tice spacings. Since the Li and transition metal slabs alternatively
stack along the [001] direction, they are overlapped and no longer
show the layered feature when viewed along the [2
21] zone axis,
as shown in Figure 5d (extracted from Fig. 4d). Coincidentally,
HRTEM images of the layered phase, viewing down the [2
21]
zone axis, have the similar lattice appearance as the rock-salt
phase along the [110] zone axis. To further confirm this feature,
we performed HRTEM image simulations of the layered phase
along the [2
21] zone axis. As can be seen from Figures 5d and 5e,
the experimental and simulated HRTEM images match very well.
The well-shaped low-thickness particles have been repeatedly
observed in pristine NCA specimens sectioned with ultra-
microtome, as demonstrated in Figures 5f and 5g and our previ-
ous work (Zhang et al., 2017b, 2017c). Figure 5f is obtained from
the bulk area of a primary particle that is ∼100 nm from the out-
ermost surface, revealing a clear atomic resolution of over
∼2.19 Å. Figure 5g is obtained ∼70 nm from the outermost sur-
face, showing an atomic resolution of ∼2.95 Å. As illustrated in
Figure 5, lattice points with the separation of 2.19 Å can be easily
resolved in the ultra-microtome sectioned cathode. In view of the
clear image contrast, a point resolution better than 2.19 Å can be
expected with ultra-microtome sectioned samples.
Here, we used the industrial-level NCA cathode to demon-
strate the capability of ultra-microtome in reducing the particle
thickness. These potato-like cathode particles have the size rang-
ing from ∼300 nm to 1 μm, for which HRTEM imaging is limited
to the surface region of 5–20 nm without access to the core area of
primary particles (Hwang et al., 2014; Karki et al., 2016; Zhang
et al., 2017a), as shown in Figure 5h.
Figure 5i shows a STEM-HAADF image of the pristine NCA
material cut with ultra-microtome, which shows a clear atomic
 Microscopy and Microanalysis 5

Fig. 3. An overview of the TEM sample prepared with ultra-microtome. (a) SEM image showing epoxy slices placed on a TEM grid. (b) Magnified view of cathode
materials imbedded in the epoxy slice. (c) Further zoom-in view showing the primary particles in the epoxy slice.

Fig. 4. Atomic-resolution imaging throughout the cathode particle. (a) Zoom-out TEM image of a cathode particle sectioned with ultra-microtome, showing a uni-
form reduction in thickness. (b–e) Zoom-in HRTEM views obtained progressively from surface toward the core, showing atomic resolution across the particle.

resolution of the R
3m layered phase (same as the one in Figs. 5f, Mechanical Effects of the Ultra-Microtome Cutting
5g). Figure 5i is obtained from a region that is ∼30 nm away from
Due to the mechanical nature of the ultra-microtome cutting,
the outermost surface, indicating that specimens prepared with
there are concerns on the possibility of generating artifacts such
the ultra-microtome method are also suitable for atomic STEM
as cracking and nanoporosity. To clarify this aspect, Figure 7 stud-
imaging. On the other hand, due to the epoxy used for particle
ies the influence of ultra-microtome on the porosity of cathode
imbedding during the sample preparation, a large amount of
particles. Figures 7a to 7c present zoom-in SEM views showing
hydrocarbon compounds is present around the NCA particles.
the primary particles in (1) the pristine material, (2) a 1-cycle
These compounds act as a source of carbon, which generates con-
electrode without ultra-microtome cutting, and (3) a 1-cycle elec-
tamination when illuminated under the electron beam irradiation
trode after ultra-microtome cutting (obtained from a microtome
and prevents clear atomic-resolution STEM imaging. To eliminate
slice). The SEM images are converted into binary images to per-
this contamination, the specimen needs to be beam-showered or
form porosity analysis, as presented in Figures 7d to 7f, respec-
plasma-cleaned.
tively. The images in Figures 7a to 7c cover the area of several
Besides the NCA cathode, the ultra-microtome is also shown
micrometers and contain thousands of primary particles for
to be capable of yielding well-sectioned TEM specimens with
obtaining statistically significant results of the porosity. The
NMC811 cathode particles. Figure 6a presents a zoom-out TEM
white areas in the binary images correspond to the cathode mate-
view of NMC811 particles sectioned with the ultra-microtome.
rial, while the black areas represent voids and electrolyte.
The relatively uniform image contrast across the particle indicates
The analysis of the binary images (Figs. 7d–7f) indicates that
the evenly reduced thickness of the particle. Figures 6b and 6c are
the concentrations of cathode particles (active material) in the
obtained from regions that are ∼80 and ∼200 nm away from the
three samples are 88.75±0.06, 69.33±0.02, and 65.11±0.04%, as
outermost surface of the particle. The lattice-resolved HRTEM
shown in Figure 7g. As can be seen, the particle concentrations
images confirm that the ultra-microtome is capable of providing
in the assembled electrodes are largely reduced compared with
TEM specimens suitable for atomic-scale imaging from the differ-
the as-received pristine material. On the other hand, the particle
ent depths of the sectioned NMC811 particles without inducing
concentrations in the uncut and cut electrodes are almost the
any noticeable mechanical damage to the crystal lattice.

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 6 H. Zhang et al.

Fig. 5. HRTEM observations of the R3m
layered phase enabled with ultra-microtome. (a,b) HRTEM view and schematic along the [010] zone axis of the layered
phase. (c) Lower-resolution image of the layered phase, where the atomic resolution is not obtained but fringes showing the layered feature are still visible.
(d,e) HRTEM view and the corresponding HRTEM simulation along the [22
1] zone axis of the layered phase. (f,g) HRTEM image from the core region of primary
NCA particles, enabled with ultra-microtome cutting. (h) HRTEM image of an uncut particle, showing no atomic resolution from the core area. (i) Atomic
STEM-HAADF image of a particle cut with ultra-microtome.

Fig. 6. Sectioning NMC811 with ultra-microtome. (a) Zoom-out TEM view of NMC811 NPs. (b,c) HRTEM images obtained from different depths of the particle shown
in (a), confirming that well-defined atomic resolution can be achieved from the core of the particle.

same. The reduction in the particle concentration during the
preparation of electrodes can be attributed to the addition of elec-
trolyte and binder (Nanda et al., 2011; Xiao et al., 2012), as sche-
matically shown in Figure 7h. The almost unchanged particle
concentration between the uncut and cut electrodes indicates
that ultra-microtome sectioning does not generate any observable
mechanical defects, such as microcracks and cavities. Otherwise,
the particle concentration in the electrode after cutting (Figs. 7c,
7f) should be significantly reduced.
The influence of the ultra-microtome cutting on the size of the
primary particles is also analyzed, as shown in Figure 8. Figures 8a
and 8c present representative SEM images of uncut and cut
1-cycle electrodes, showing primary particles embedded in the
electrolyte and binder. Figure 8a is obtained from the raw elec-
trode, and Figure 8c is obtained from an epoxy slice sectioned
from the electrode. The morphology and size distribution of the
primary particles in the microtome-sectioned electrode is almost
the same as the uncut electrode. This is supported by comparing

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 Microscopy and Microanalysis 7

Fig. 7. The influence of the ultra-microtome cutting on the porosity of cathode materials. (a–c) SEM images showing the primary particles of the pristine material, a
1-cycle electrode without ultra-microtome cutting, and a 1-cycle electrode after ultra-microtome cutting. (d–f) Binary images converted from the SEM images
shown in (a–c), respectively. The white areas correspond to the cathode material, and the black areas correspond to voids and electrolyte. (g) Histogram showing
the particle concentrations in the three samples shown in (a–c). (h) Schematic showing the cathode particles mixed with electrolyte and binder in the battery
electrode.

the particle size distribution of the two samples. The particle sizes
were manually measured by excluding aggregated ones in Figures
8a and 8c, and the histograms of the size distributions are shown
in Figures 8b and 8d. Gauss fitting of the histograms yields the
mean sizes of ∼58.53 and ∼63.71 nm for the uncut and
microtome-sectioned primary particles, respectively. Their close
match indicates that the ultra-microtome sectioning does not
crush the cathode particles. Otherwise, fragments of the primary
particles are supposed to show up, and a large number of “smaller
particles” can be observed in Figures 8b and 8d.
According to the morphology analysis in Figures 7 and 8, no
observable mechanical damage is caused by the ultra-microtome
sectioning of the relatively fragile NCA cathode. Additionally, the
observed atomic configuration of the layered phase in the ultra-
microtome sample shown in Figure 5 is identical to its established
structure, meaning that ultra-microtome has not caused any
phase transformation. This argument is also supported by our
previous work, in which TEM observations of uncut and cut sam-
ples reveal the same (003) cracking (Zhang et al., 2017c) and
“anti-core-shell” phase transformation (Zhang et al., 2017b) in
the bulk of cycled NCA particles. In summary, no structural
changes caused by the ultra-microtome sectioning has been
observed at either the atomic or micrometer levels.
Challenges of the Ultra-Microtome Sectioning
Despite the high-quality ultra-microtome specimens with ignorable
mechanical artifacts, there are also several challenges that should be
taken into consideration, as presented in Figure 9. The ultra-thin
nature of the epoxy membrane makes it vulnerable to the electron
beam irradiation in TEM. The high-energy e-beam along with its
charging effect can cause vibration of the epoxy membrane, reduc-
ing the TEM resolution. To resolve this issue, a carbon coating is
mounted on the TEM copper grid to provide a stable support for
the epoxy slices. The carbon coating is usually ultra-thin (a few
nanometers) or highly porous not to jeopardize the TEM resolution.
Sometimes the high-energy e-beam even partially decomposes
and evaporates the epoxy membrane to generate holes (Fig. 9a,

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 8 H. Zhang et al.

Fig. 8. Influence of the ultra-microtome cutting on the size of the primary particles in the electrode. (a,c) Representative SEM images of the uncut and cut 1-cycle
electrodes, exhibiting similar morphologies of primary particles. (b,d) Histograms showing the size distributions of the primary particles in (a,c), indicating that the
two cathodes have primary particles with almost the same size distribution.

Fig. 9. Challenges of the ultra-microtome method for TEM specimen preparation. (a) Holes generated in the epoxy membrane by the electron beam irradiation. (b)
Carbon contamination on the surface of a 1-cycle NCA particle under STEM-HAADF imaging.

marked with orange arrows). The tension within the membrane
can cause a quick expansion of these holes, which finally destroys
the whole membrane. The generation of holes can be attenuated
by reducing the dose-rate of the e-beam and avoiding epoxy
films with the imperfections since the imperfections can be a
source for the membrane piercing. It is worth mentioning that
defective epoxy membrane areas tend to break up under the
e-beam irradiation due to stress concentrations at defect sites
such as holes and tears. Defect-free membrane areas are more
robust and preferred for TEM observations.
Another challenge of the ultra-microtome method is the car-
bon and hydrocarbon contamination of specimens. Due to the
organic nature of the epoxy membrane, it can be decomposed
by the e-beam irradiation into carbon and hydrocarbon species
(Luft, 1961; Keller et al., 2004; Monticelli et al., 2007; Griffiths
& Walther, 2010). When an intense e-beam, such as the STEM
electron probe, is applied on the cathode particle embedded in
epoxy, its strong charging effect drives the concentration of the
carbon and hydrocarbon species toward the e-beam, as marked
by the orange arrows in Figure 9b, showing up as bright spots.
The carbon and hydrocarbon contamination largely reduces the
resolution of the STEM/TEM imaging, which is largely deter-
mined by the stability of the epoxy film. In this work, the
epoxy bars were treated at 60°C for 24 h for solidification,

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 Microscopy and Microanalysis
according to its technical sheet. After treatment, the epoxy bars
were fully solidified without remaining liquids.
Carbon contamination during STEM-HAADF imaging can be
minimized by choosing an area with the intact epoxy film and
showering the area with the e-beam. As shown in Figure 5d,
atomically resolved STEM-HAADF images can be obtained
with the e-beam shower for ∼20 min under the STEM-HAADF
mode with a current intensity of ∼20 pA/(nm2 s) and an
on-screen magnification of 27,000 times, followed by
STEM-HAADF imaging using the same current intensity.
Comparison with Other Sample Preparation Methods
As discussed in the introduction section, there are multiple sam-
ple preparation methods for reducing the thickness of NPs.
Compared with the ultra-microtome cutting, these methods
exhibit both advantages and disadvantages, as discussed in the
following.
Crushing and grinding with a pestle and a mortar is the sim-
plest and cheapest way for reducing the particle size (Kisch, 1991;
Mori et al., 1999). The particles can be crushed into pieces smaller
than 50 nm, which easily meet the requirement of atomic
HRTEM imaging. However, the micrometer-scale features of the
particles are damaged during this process. Also, the grinding usu-
ally introduces a high concentration of mechanical artifacts, such
as vacancies, microcracks, dislocations, and twinning. Therefore,
it can only yield very limited information regarding the target
material.
Compared with ultra-microtome, FIB can precisely pick a spe-
cific location for TEM sampling, which is very useful for high-
accuracy microstructure characterization. The specimen prepared
with FIB is very clean and in the desirable shape, which benefits
the TEM imaging. However, it also has multiple drawbacks com-
pared with the ultra-microtome method. The largest FIB lift-out
TEM specimen is ∼10 nm in lateral, which only contains a
dozen of NPs of hundreds of nanometers. The ultra-microtome
specimen, however, can be as large as 1–2 mm in lateral dimen-
sions, which thus contains hundreds of thousands of the same
NPs. Considering a 5 μm × 5 μm FIB specimen and a 1 mm ×
0.5 mm microtome specimen, the microtome specimen is
20,000 times larger than the FIB sample. The large number of
cathode particles in the ultra-microtome specimen allows for
the statistical analysis of a large collection of particles.
Ultra-microtome also exhibits other advantages over FIB, such
as its improved time-efficiency compared with FIB. The prepara-
tion of one TEM sample with ultra-microtome usually takes less
than 20 min, while it usually takes more than 5 h for FIB. Also,
the ultra-microtome method can potentially cut relatively large
samples up to 1 mm, while FIB is not suitable for this purpose.
On the other hand, the ultra-microtome method also has
drawbacks such as the potential mechanical damage on the sam-
ple, as well as the hydrocarbon/carbon contamination due to the
use of epoxy. The high-energy ion beam of FIB largely removes
any potential hydrocarbon/carbon contamination, so the FIB
sample is usually very clean. The hydrocarbon contamination of
the ultra-microtome sample cannot be removed, meaning that it
may not be suitable for in situ TEM experiments.
Considering the advantages and drawbacks of different TEM
specimen preparation methods, it is important to select the
appropriate method depending on the specific conditions of the
sample and the observation requirements. In Figures 4 to 7, we
have demonstrated that the major potential drawbacks of the
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9
ultra-microtome cutting (mechanical effect and introduction of
hydrocarbon) can be minimized without introducing artifacts to
the microstructural feature of the cathode material while still
achieving the atomic resolution of TEM imaging. Based on
these observations, it can be concluded that ultra-microtome is
a suitable method to prepare TEM specimens and reveal the
atomic feature in the NCA cathode.
Conclusion
An ultra-microtome-based method for the preparation of TEM
specimens is introduced for sectioning particles of the cathode
material of Li-ion batteries. The specimens prepared by the
microtome method contains a large number of the sectioned par-
ticles that are sufficiently thin to yield atomic-scale HRTEM and
STEM imaging of the microstructural feature. No observable
structural damages or artifacts, including lattice amorphization,
microcracking, or fragmentation, are introduced from the micro-
tome sectioning. This ultra-microtome-based method can find
broader applicability in the preparation of the TEM specimens
from particulate matter of varying size ranges.
Acknowledgments. This work was supported as part of the NorthEast
Center for Chemical Energy Storage (NECCES), an Energy Frontier
Research Center funded by the U.S. Department of Energy, Office of
Science, Basic Energy Sciences under Award # DE-SC0012583. The TEM
work was conducted in the William R. Wiley Environmental Molecular
Sciences Laboratory (EMSL), a national scientific user facility sponsored by
DOE’s Office of Biological and Environmental Research and located at
PNNL. PNNL is operated by Battelle for the Department of Energy under
Contract DE-AC05-76RLO1830. C.M.W. is supported by the Assistant
Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle
Technologies of the U.S. Department of Energy under the advanced cathode
materials program.
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