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Article
Carbon-black-based self-standing porous
electrode for 500 Wh/kg rechargeable lithium-
oxygen batteries
Shoichi Matsuda, Eiki Yasukawa,
Takashi Kameda, Shin Kimura,
Shoji Yamaguchi, Yoshimi Kubo,
Kohei Uosaki

matsuda.shoichi@nims.go.jp

Highlights
Operation of 500 Wh/kg class
rechargeable lithium-oxygen
battery at 0.1 C-rate

Self-standing carbon membrane

with hierarchical meso-/
macroscale pore structure

Discharge capacity of 7,000 mAh/

gelectrode was achieved at current
density of 0.4 mA/cm2

Advanced cell design for

minimizing the weight of inactive
components

Matsuda et al. develop a carbon black powder-based self-standing membrane

with hierarchical meso-/macroscale pore structure. Using this carbon membrane as
positive electrode, a 500-Wh/kg class rechargeable lithium-oxygen battery is
fabricated and a repeated discharge/charge cycle is demonstrated at a 0.1 C-rate.

Matsuda et al., Cell Reports Physical Science 2,

100506
July 21, 2021 ª 2021 The Author(s).
https://doi.org/10.1016/j.xcrp.2021.100506
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Article
Carbon-black-based self-standing
porous electrode for 500 Wh/kg
rechargeable lithium-oxygen batteries
Shoichi Matsuda,1,2,3,* Eiki Yasukawa,1,2 Takashi Kameda,1,2 Shin Kimura,1,2 Shoji Yamaguchi,1,2
Yoshimi Kubo,1,2 and Kohei Uosaki1,2

SUMMARY
While lithium-oxygen batteries exhibit high theoretical energy den-
sities that by far exceed those of conventional lithium-ion batteries,
there are a limited number of examples that actually demonstrate
cells with high energy density. The limitation of the positive elec-
trode with a capacity high enough to sustain repeated discharge/
charge cycles under high areal capacity conditions hinders the im-
plementation of the lithium-oxygen batteries with practically high
energy density. In this study, we develop a carbon black powder-
based self-standing membrane, which exhibits a discharge capacity
of ~7,000 mAh/gelectrode even under high current density conditions
(>0.4 mA/cm2). Using the developed self-standing carbon mem-
brane as the positive electrode, a 500-Wh/kg class rechargeable
lithium-oxygen battery was fabricated and a repeated discharge/
charge cycle was demonstrated at 0.1 C-rate. The results obtained
in this study provide new material research directions to realize
high energy density rechargeable lithium-oxygen batteries and
facilitate their future development.

INTRODUCTION
There has been considerable interest in developing rechargeable lithium-oxygen (Li-
O2) batteries, which have the potential for exceeding the limit of energy density in Li-
ion batteries (~300 Wh/kg).1–4 In typical cell configurations of Li-O2 batteries,
porous carbon membranes and Li foils are used for the positive and negative elec-
trodes. During discharge, atmospheric oxygen is reduced in the pores of the carbon
electrode and combines with Li ions to form solid lithium peroxide (Li2O2) as the
product (O2 + 2Li+ + 2e / Li2O2). Furthermore, the anodic dissolution of Li-metal
occurs at the negative electrode (Li / Li+ + e ). In the charging process, the revers-
ible reaction should occur at both electrodes. To realize Li-O2 batteries with practi-
cally high energy density, an improvement in the positive electrode performance is
required. In particular, the hierarchical pore structure of the carbon electrode should
1Center for Green Research on Energy and
be designed properly. In the positive-electrode reaction, Li2O2 generated during
Environmental Materials, National Institute for
the discharge process accumulates on the pores of the carbon electrode. Thus, Material Science, 1-1 Namiki, Tsukuba, Ibaraki
the carbon electrode is required to ensure sufficient pore capacity for storing depos- 305-0044, Japan
ited Li2O2.5–7 In addition, for efficient oxygen reduction under relatively high current 2NIMS-SoftBank Advanced Technologies
Development Center, National Institute for
density conditions, interconnected micron-sized macropores should be formed, Material Science, 1-1 Namiki, Tsukuba, Ibaraki
which can enhance the oxygen transport through the carbon electrode.8–12 305-0044, Japan
3Lead contact
Among the carbon materials, electrodes based on carbon nanomaterials, such as *Correspondence: matsuda.shoichi@nims.go.jp
carbon nanotubes (CNTs) and graphenes, showed excellent performance as a https://doi.org/10.1016/j.xcrp.2021.100506

Cell Reports Physical Science 2, 100506, July 21, 2021 ª 2021 The Author(s). 1
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
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positive electrode in Li-O2 batteries.13–18 In addition to their high specific surface

area, free-standing membranes can be fabricated without using a polymetric binder,
thereby maximizing the carbon content of the electrode. In fact, the superior perfor-
mance of >4,000 mAh/g was reported at a high current density of 0.6 mA/m2.14
However, the CNT or graphene-based positive electrodes have limitations of mate-
rial cost, which hinder their practical application in Li-O2 batteries.

Compared to the carbon nanomaterials, carbon black has a low materials cost and a
high specific surface area, thus making it an alternative material for positive elec-
trode in Li-O2 batteries. In addition, there are various types of commercially avail-
able carbon black powders with different pore structures, which contribute to the
high design flexibility for the pore structure of carbon electrodes. In fact, previous
studies demonstrated a high capacity of >5,000 mAh/g.19–23 However, such a supe-
rior capacity was obtained only at a current density of <0.1 mA/cm2. Furthermore,
because the carbon black powders do not have sufficient mechanical strength to
stand alone as a self-standing membrane, it is necessary to use a large amount of
binder and substrate material for preparing the electrode. However, such inactive
components in the electrode decrease the capacity per electrode mass (mAh/
gelectrode).

In this study, we developed a carbon black powder-based self-standing membrane

for the positive electrode of Li-O2 batteries that exhibit high capacity at high current
densities. In particular, a porous carbon electrode was designed to minimize the
ratio of non-active materials—binder and substrate—to maximize the ratio of the
carbon black powder in the electrode. As a result, we successfully fabricated the car-
bon-black-based self-standing membrane, which consists of >70% carbon black
powder, exhibiting a capacity of >7,000 mAh/gelectrode at a current density of 0.4
mA/cm2, which is the best performance of the carbon-black-based electrode.

RESULTS AND DISCUSSION

Energy density simulation of Li-O2 batteries
We investigated the effect of the capacity of the carbon electrode (mAh/gelectrode) on
the energy density of Li-O2 batteries. The parameters of the Li-O2 battery compo-
nents used in our simulation are listed in Table S1 and the simulated energy densities
of the Li-O2 battery are shown in Figure 1A. The energy density was calculated based
on the following conditions: areal capacity of 3.0 mAh/cm2 and average discharge
voltage of 2.7 V, respectively. The areal capacity of the carbon electrode was
adjusted to 6.0 mAh/cm2, which is 2 times higher than that of the areal capacity
for the cycling test of 3.0 mAh/cm2, by changing the mass loading of the carbon elec-
trode (mg/cm2) (Table S1). The porosity of the carbon electrode and the density of
the electrolyte were set at 95% and 1.1 g/cm3. When a carbon electrode with a ca-
pacity of 2,000 mAh/gelectrode was used, the energy density of the Li-O2 battery was
<192 Wh/kg (black squares in Figure 1A). The percentage of the cell component is
shown in Figure 1B. It can be seen that the weights of the electrolyte in the carbon
electrode account for 78.4% of the total weight (Figure 1B). A large amount of elec-
trolyte is required to fully fill the pore space of the carbon electrode, decreasing the
energy density of the cell. For Li-ion batteries, the ratio of electrolyte weight to cell
capacity (E/C, g/Ah) was used as the empirical parameters for representing the elec-
trolyte amount. When the carbon electrode with the capacity of 2,000 mAh/gelectrode
was used with 100% electrolyte injection into the carbon electrode, the E/C ratio was
10.7 g/Ah, which is significantly smaller than those reported in previous studies (E/C
R50 g/Ah).24 Here, assuming that the filling rate of the electrolyte inside the carbon

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A B C

Figure 1. Energy density simulation of lithium-oxygen batteries

(A) Relationships between energy density and capacity for the carbon electrodes with different electrolyte injection ratio.
(B and C) Weight fractions of lithium-oxygen cell components calculated using the parameters listed in Table S1.
(B) Capacity of carbon electrode = 2,000 mAh/g electrode and electrolyte injection ratio in carbon electrode = 100%.
(C) Capacity of carbon electrode = 6,000 mAh/g electrode and electrolyte injection ratio in carbon electrode = 60%.

electrode is 60%, the energy density is increased to 274 Wh/kg; however, it is still
<300 Wh/kg (blue triangle in Figure 1A). When a carbon electrode with a capacity
of 6,000 mAh/gelectrode was used with 60% electrolyte injection into the carbon elec-
trode, the energy density exceeded 500 Wh/kg (blue triangle in Figure 1A). In this
case, the weight of the electrolyte in the carbon electrode was reduced to 44.2%
(Figure 1C), thereby resulting in a breakdown of the total weight of the cell. Further-
more, the E/C value reached 2.3 g/Ah. The results obtained by these simulations re-
vealed the importance of increasing the energy capacity of the carbon electrode
(mAh/gelectrode) for maximizing the energy density of Li-O2 batteries.

Carbon-black-based self-standing membrane for Li-O2 batteries

As a method for preparing a self-standing carbon membrane with a connected pore
structure, which provides mass transport channels through the electrode, we
focused on the use of a non-solvent-induced phase separation method.25 The phase
separation method is a technique for producing a porous membrane that uses the
difference in solubility of polymer materials in a solvent as a driving force for pore
structure formation. By mixing carbon black powders, a carbon fiber, and a polymer
material as a film-constituting element, a carbon-based self-standing membrane can
be prepared. In this case, the carbon fiber was used for improving the mechanical
strength of the prepared membrane. The polymer material functions as an adhesive
between the carbon particles. Considering the instability of the fluorine-based
binder under the operating conditions of the Li-O2 battery,26 Polyacrylonitrile
(PAN) was selected as the polymer material, which can be finally converted to carbon
through heat treatment under inert conditions. For the carbon black powder, Ketjen-
black (KB) is used owing to its high surface area. A slurry containing a suitable ratio of
the polymer and carbon material was prepared and formed into a membrane by a
doctor blade (Figure 2A). For the non-solvent phase separation method, we used
N-methyl-2-pyrrolidone (NMP) and MeOH as the rich and poor solvents, respec-
tively. For increasing the content of KB, which functions as an electrochemical reac-
tion site, the ratio of PAN and carbon fiber is preferably reduced as much as possible.
However, if the ratio of PAN and carbon fiber is too low, the mechanical strength of
the formed carbon membrane is insufficient and the membrane cannot remain in a

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A B C

D E

Figure 2. Carbon-black-based self-standing membrane

(A) Schematic illustration of synthetic procedure of carbon-black-based self-standing membrane.
(B–E) Photograph (B) and (C–E) SEM image of KB-based free-standing membrane.

self-standing structure. In the present study, a mixture slurry was prepared using 65
wt% of KB, 12 wt% of carbon fiber, and 23 wt% of PAN. The prepared membrane was
dried and heat treated under suitable conditions, and finally calcinated at 1,050 C in
an inert atmosphere. A self-standing carbon membrane was obtained (Figure 2B).

Figure 2C shows the cross-sectional scanning electron microscopy (SEM) image of

the porous carbon membrane, revealing its self-standing property with a thickness
of ~270 mm. From the high-magnification SEM images, it can be seen that the KB
particles are uniformly distributed in the membrane (Figures 2D and 2E). The
elemental composition of the membrane was investigated by X-ray photoelectron
spectroscopy (XPS) (Table S2). Although the carbon content in the membrane was
>97 wt%, 1.7 wt% of nitrogen—originating from PAN—was detected. The electrical
conductivity of the membrane was evaluated by the 4-terminal method, revealing a
resistivity of 0.15 U cm, which is sufficiently low for using a positive-electrode mate-
rial in Li-O2 batteries. The porosity of the porous carbon membrane was 91.3%,
which was calculated from the weight and thickness of the membrane. The details
of the pore structure were analyzed by nitrogen adsorption measurements. Figure 3
shows the pore size distributions obtained from nitrogen adsorption measurements
of the KB powder (black curve in Figure 3A) and KB-based self-standing membrane
(black curve in Figure 3B). It can be seen that the KB self-standing membrane has a
mesoscale pore volume of 1.3 cm3/g, which corresponds to a 70% pore volume of
the KB powder. This result is consistent with the fact that the KB ratio in the self-
standing membrane is ~70%. Importantly, it can be observed that the pore structure
of the KB-based self-standing membrane reflects the characteristics of the pore
structure of the carbon black powder (black curves in Figures 3C and 3D).

To evaluate the performance of the prepared free-standing carbon membrane as a

positive-electrode material for Li-O2 batteries, we assembled a Li-O2 cell and inves-
tigated its discharging property. The cell consisted of a Li foil, glass fiber separator,
and free-standing carbon membrane with a thickness and carbon loading of 270 mm
and 5.4 mg/cm2, respectively. The details are described in the Experimental

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A B

C D

Figure 3. Microporous/mesoporous structures analyses

Change in pore volume with respect to pore size for (A and C) KB powder and (B and D) KB-based
free-standing membrane without (black line) and with (red line) the oxygen treatment process. The
results are obtained by evaluation through the nitrogen adsorption method.

procedures. Figures 4A and S1 show the representative discharge profile of the Li-O2
cell. The cell exhibited a stable voltage plateau at ~2.8 V and finally showed a gradual
decrease in voltage, which is a typical discharge profile of Li-O2 batteries. A discharge
capacity of 3,313 mAh/gelectrode was exhibited at a current density of 0.05 mA/cm2
and a cutoff voltage of 2.3 V. Even under a current density of 0.4 mA/cm2, the cell
showed a relatively high discharge capacity of 2,488 mAh/gelectrode. Figure S2 shows
the pore size distributions of the carbon electrode after discharging at a current den-
sity of 0.05 mA/cm2. The amount of mesoscale pore volume significantly decreased
from 1.4 to 0.4 cm3/g. The results suggest that the mesoscale pore is mainly used for
the accumulation of Li2O2 during the discharge process, which is also suggested by
previous studies.5,6,9,10

Furthermore, we performed the discharge/charge cycle tests of the Li-O2 batteries.

To minimize the undesired influence of the Li-metal negative electrode, a ceramic-
based solid-state separator was used to protect the Li-metal negative electrode.
The details of the Li-O2 cell are shown in Table S3 and Figure S3. For the
discharge/charge cycle test, we used electrolyte containing dual anion redox medi-
ator, which was reported to realize relatively high reaction efficiency in both positive
and negative electrodes.27,28 Figures 5A and S4 show the discharge/charge profile
of the Li-O2 cell with a capacity limitation of 4.0 mAh/cm2. The cell exhibited a stable
voltage plateau at ~2.65 V during the discharging process. During charging, the cell
exhibited a stable voltage plateau at ~3.5 V and gradually increased to 4.0 V, which
is the typical charging profile of Li-O2 batteries using electrolyte containing redox
mediator. The reversible formation/decomposition of Li2O2 during the discharge/
charge process was confirmed by X-ray diffraction (XRD) analysis of the electrodes
(Figure S5). A stable discharge/charge reaction occurred during the 1–30 cycles.
The increase in overpotential in both the discharging and charging process can be
observed during the repeated cycles, and the discharge voltage reached its cutoff
voltage at the 37th cycle (pink curve in Figure 5A). We consider that this increase
in the overpotential originated from the accumulation of solid-state side products
on the surface of the carbon electrode, which is induced by the decomposition of
the electrolyte components. The formation of Li-carbonate-like side products and

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A C

Figure 4. Discharge performance tests of lithium-oxygen batteries

(A and B) Discharge profile of lithium-oxygen cells using KB-based self-standing carbon membrane
(A) without and (B) with the oxygen treatment process as positive-electrode material. The current
densities are 0.05 mA/cm 2 (black curve), 0.4 mA/cm 2 (red curve), 0.6 mA/cm 2 (green curve), and 0.8
mA/cm 2 (blue curve).
(C) The relationship between discharge capacity and current density during the discharge process
of lithium-oxygen cells using the KB-based self-standing carbon membrane without (black curve)
and with (red curve) the oxygen treatment process as positive electrode material. Mass loading of
electrode is 5.4 (black triangle), 3.4 (red triangle), 2.0 (red circle), and 1.4 mg/cm 2 (red square). The
error bars in (C) denote the standard deviation of three technical replicates.

pore clogging of the carbon electrode was confirmed by nitrogen adsorption mea-
surement and attenuated total reflection-infrared spectroscopy (ATR-IR) analyses
(Figures S6 and S7). Although the E/C value in this cell is 7.1 g/Ah, which is much
smaller than those reported in previous studies,29–33 based on our energy density
simulation (Figure 1), the E/C value should be further reduced to realize the Li-O2
cell with an energy density >300 Wh/kg. Furthermore, the ceramic-based Li-ion
conductor is used as a protective layer for the Li-metal negative electrodes; howev-
er, the large weight of this component influences the total weight of the Li-O2 cell,
therefore resulting in an energy density of <200 Wh/kg (Table S3).

Here, we focused on the relationship between the thickness (carbon loading) of the self-
standing carbon membrane and the discharge performance. In our method, the thick-
ness (carbon loading) can be tuned by controlling the amount of coated slurry. Figure S8
shows the discharge profiles of the Li-O2 cells containing the self-standing membranes
with thicknesses of 140 and 80 mm, in which the carbon loading values were 2.8 and
1.4 mg/cm2, respectively. Under conditions of current density of 0.05 mA/cm2, an in-
crease can be seen in the discharge capacity per weight of the carbon electrode
(mAh/gelectrode) by decreasing the thickness (carbon loading) of the membrane (black
curves in Figure S5). In contrast, at a current density of 0.4 mA/cm2, the enhancement
of the discharge capacity was limited (red and green curves in Figure S8).

To further improve the discharge capacity, particularly at high current density condi-
tions, we focused on decreasing the amount of PAN-derived carbon, which does not
function as an electrochemical reaction site. However, if the proportion of PAN is
reduced during slurry preparation (before the membrane structure is formed), the
finally obtained carbon membrane does not possess sufficient mechanical strength
to maintain its self-standing property. Considering the function of PAN, ideally, PAN
should exist at the interface of the KB particles, which contributes to improving the
adhesion of the KB particles, resulting in the improved mechanical strength of pre-
pared membrane. However, in reality, a certain amount of PAN is also located on the

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A B C

Figure 5. Discharge/charge performance tests of lithium-oxygen batteries

(A) Discharge/charge profile of lithium-oxygen cells using KB-based self-standing carbon membrane without the oxygen treatment process as positive
electrode. The limiting capacity and cutoff voltage were set to 4.0 mAh/cm 2 , 2.0 V/4.2 V. The current density during discharging and charging process
was set to 0.4 and 0.2 mA/cm 2 .
(B) Discharge/charge profile of lithium-oxygen cells using KB-based self-standing carbon membrane with the oxygen treatment process as positive
electrode. The current density, limiting capacity, and cutoff voltage were set to 0.3 mA/cm 2 , 3.0 mAh/cm 2 , 1.5 V/4.2 V.
(C) The energy density (black line) and charging efficiency (blue line) of 500 Wh/kg class lithium-oxygen cell.

inside of the KB particles, decreasing the effective electrochemical surface area of

the carbon membrane. Based on these considerations, we focused on the removal
of part of the PAN existing inside of the KB particles without diminishing the me-
chanical strength of the prepared membrane. Experimentally, this can be realized
by performing an oxygen treatment process. In this process, the membrane was
treated with a small concentration of oxygen at a suitable temperature to selectively
decompose the PAN existing inside of the KB particles. Such an oxygen treatment
process (calcination at 600 C in 0.1% oxygen atmosphere) was performed after
the carbon skeleton structure was formed by converting the PAN polymer to the sta-
bilized state of PAN by calcination at 230 C in air (Figure 2A). It should be noted that
such a complicated and high-temperature process is not suitable from the viewpoint
of industrial commercialization and should be replaced by much simpler and more
cost-effective procedures in the near future.

The physical properties of the oxygen-treated KB-based self-standing membrane were

investigated and are shown in Table S2. Compared to the sample prepared without
the oxygen treatment process, the sample prepared using the oxygen treatment process
showed a lower yield and lower nitrogen content, although the thickness of the mem-
brane was almost the same. These results clearly suggest that PAN-derived carbon
was removed by the oxygen treatment process. As a result, the porosity of the membrane
increased from 91.3% to 94.1%. The pore size distributions of the oxygen-treated carbon
membranes are shown in Figure 3 (red lines in Figures 3B and 3D). It is observed that the
pore volume increased from 1.3 to 2.4 cm3/g by performing oxygen treatment. Notably,
the oxygen-treated carbon membranes possessed a higher pore volume than the KB
powder itself, thereby suggesting that the pore structure of KB is also modified by the ox-
ygen treatment process. Figure S9 shows the results of the transmission electron micro-
scopy (TEM) of the electrode. It can be seen that the size of the KB particles decreases with
oxygen treatment. Considering the fact that such a change does not occur when the KB
powder is simply treated with oxygen, the increase in the pore size of the membrane pro-
ceeds associated with the disappearance of PAN during the oxygen treatment process.
Figure S10 shows the results of mercury porosimetry. It can be seen that the macroscale
pore (0.1–10 mm) volume also largely increases from 1.8 to 3.6 cm3/g by performing the
oxygen treatment process. These results suggest that the oxygen treatment process is an
effective method for increasing both mesoscale and macroscale pores.

Figures 4B and S11 shows the discharge profile of the Li-O2 cells with the oxygen-treated
carbon membranes with a thickness of 260 mm, exhibiting a discharge capacity of 4,813

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mAh/gelectrode at the current density of 0.4 mA/cm2. This value is ~1.6 times higher than
those of the sample with the same thickness without an oxygen treatment process. By
decreasing the thickness of the membrane, an improvement in the discharge capacity
per weight of carbon was observed. In particular, the sample with a thickness of
140 mm exhibited discharge capacities of 7,148 mAh/gelectrode at current densities of
0.4 mA/cm2 (Figures S12 and S13). The relationships between the discharge capacity
(mAh/gelectrode) and the areal current density (mA/cm2) are shown in Figure 4C. In all
of the current density regions, the discharge capacity increases with oxygen treatment.
In addition, the further enhancement of the discharge capacity was achieved by
decreasing the thickness of the carbon membrane. Notably, such an enhancement effect
was observed even in the high current density regions (>0.6 mA/cm2). An increase in the
macroscale pore volume is considered to contribute to improving the oxygen transport
property, thereby resulting in an increase in the discharge capacity under high current
density conditions.

Li-O2 batteries with energy density of 500 Wh/kg

Using the carbon electrode developed in this study, a 500-Wh/kg class Li-O2 cell was
fabricated and its discharge/charge property was evaluated. The details of the cell
components are listed in Table S3. In this experiment, we used an oxygen-treated
carbon membrane with a thickness and carbon loading of 100 mm and 1.0 mg/
cm2, respectively. The current density and areal capacity were set to 0.3 mA/cm2
and 3.0 mAh/cm2, resulting in the E/C value of 2.7 g/Ah. Figures 5B and S14 show
the discharge/charge profile of the 500 Wh/kg class Li-O2 cell. The cell exhibited
a stable voltage at ~2.65 V during the discharging process. Furthermore, the cell
also exhibited a typical charging profile of Li-O2 batteries. The initial charging
voltage is ~3.2 –3.5 V and gradually increases to 4.0 V. Although the stable
discharge/charge reaction occurred during 1–4 cycles, the charging efficiency drop-
ped to 60% in the 5th cycle and 40% in the 6th cycle (blue circles in Figure 5C). As a
result, there was a decrease in the discharge voltage at the 6th cycle. At 7th cycles,
the discharge voltage reached a cutoff condition of 1.5 V. In addition to the side re-
actions on the positive electrode side, such as decomposition of electrolyte34,35 and
the accumulation of Li-carbonate-like solid-state side product on the carbon elec-
trode,36,37 we consider that the deterioration of the negative electrode side also
should be taken into account.38,39 The SEM analysis of the negative electrode after
the cycling test revealed that only part of the metallic Li remains on the electrode
(Figure S15). We confirmed that the porous structured Li was accumulated on the
surface of the negative electrode, which was easily broken during the cell electrode
washing process and cannot be observed by SEM analysis. The advanced analytical
technique should be adopted to deepen our understanding of the degradation
mechanism of the 500 Wh/kg class Li-O2 cell. Further enhancing the cycle life of
Li-O2 batteries is the focus of the ongoing research in our laboratory.

In summary, we developed a carbon black powder-based self-standing membrane

for use as an electrode material for Li-O2 batteries with a high energy density. Using
non-solvent phase separation techniques and the oxygen treatment process, we
successfully fabricated a carbon-black-based self-standing membrane, which con-
sisted of >70% carbon black powder. The self-standing membrane exhibited a ca-
pacity of >7,000 mAh/gelectrode at a current density of 0.4 mA/cm2, which is the
best performance among the carbon-black-based electrodes. Although previous
studies already reported the high-capacity KB-based electrode for Li-O2 batteries
in terms of capacity per weight of carbon (mAh /gcarbon),19–23 but the reports are
very limited in terms of capacity per weight of carbon (mAh /gelectrode). Using the car-
bon electrode developed in this study, a Li-O2 cell with an energy density of 500 Wh/

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kg was fabricated and a repeated discharge-charge cycle was demonstrated at a 0.1

C-rate. To our knowledge, this is the first demonstration of the operation of 500 Wh/
kg class Li-O2 batteries at room temperature.40–42 The strategy for preparing the car-
bon black powder-based self-standing membranes provides new research direc-
tions for realizing high energy density, rechargeable Li-O2 batteries.

EXPERIMENTAL PROCEDURES
Resource availability
Lead contact
Further information and requests for resources should be directed to and will be ful-
filled by the lead contact, Dr. S. Matsuda (matsuda.shoichi@nims.go.jp).

Materials availability
This study did not generate new unique reagents.

Data and code availability

All of the data associated with this study are included in the article and supplemental
information. Additional information is available from the lead contact upon reason-
able request.

Preparation of carbon black powder-based self-standing carbon membrane

A mixture slurry was prepared using 65 wt% of KB (Lion Specialty Chemicals,
EC600J), 12 wt% of carbon fiber (average fiber diameter of 6 mm and average length
of 3 mm), 23 wt% PAN, and NMP as a solvent for uniform dispersion. The mixture
slurry was formed into a sheet by molding to a uniform thickness by a wet film-form-
ing method using a doctor blade. After molding, the sample was immersed in meth-
anol (poor solvent) and converted to a porous film by the non-solvent-induced phase
separation method. Furthermore, a volatile solvent was removed by drying the sam-
ple at 80 C for 10 h; subsequently, heat treatment was performed (infusibilization
treatment) at 230 C for 3 h in the atmosphere using a box-type furnace (Denken
High Dental). With the oxygen treatment process, the membrane was treated with
0.1% oxygen in a nitrogen atmosphere by raising the temperature to 600 C at a
rate of 10 C/min and maintaining the temperature at 600 C for 0.5 h. Carbonization
was performed by raising the temperature to 1,050 C at a rate of 10 C/min and
maintaining the temperature of 1,050 C for 3 h and then allowing the sample to
cool to room temperature. In all cases, the flow rate of gas was set to 800 mL/min.

Characterization of carbon black powder-based self-standing carbon

membrane
Microporous/mesoporous structures of the samples were characterized by nitrogen
adsorption (3 FLEX, Micromeritics Instruments). Macropore size distributions were
measured by mercury porosimetry (AutoporeIV 9505, Shimadzu). Field-emission
SEM (FE-SEM, S-4800, Hitachi) and SEM-energy-dispersive spectroscopy (EDS)-
electron backscatter diffraction (EBSD) (JSM-7800F, JEOL), and XRD (SmartLab, Ri-
gaku) were used to characterize the discharge products. Before the SEM, XRD, and
Fourier transform IR (FTIR) analyses, the positive electrodes were removed from the
electrochemical cells after the discharging process, washed three times with aceto-
nitrile, and dried under vacuum. During sample preparation, the samples were not
exposed to ambient atmosphere.

Li-O2 cell assembly and discharge performance test

A solution of 1 M Li trifluoromethanesulfonate (LiTfO; Kishida Chemical, purity
>99.9%) dissolved in tetraethylene glycol dimethyl ether (tetraglyme; Kishida

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Chemical, purity >99%) was used as the electrolyte. The water content of the
electrolyte was <30 ppm and was measured by Karl Fischer titration. The carbon
electrode was dried at 100 C under vacuum for 12 h. Coin-type Li-O2 cells were
assembled in a dry room with a water content of <10 ppm by sequential stacking
of metallic Li foil (diameter = 16 mm, thickness = 0.2 mm; Honjo Metal), a glass fi-
ber-based separator (diameter = 18 mm, thickness = 0.27 mm; Whatman GF-A), a
carbon electrode (diameter = 16 mm, thickness = 0.27 mm), and a gas diffusion layer
(diameter = 16 mm, thickness = 0.19 mm; TGP-H-060, Toray). During assembly,
100 mL of the electrolyte was added to the separator. Electrochemical experiments
were conducted using battery-test equipment (SD8, Hokuto Denoko).

Li-O2 cell assembly and discharge/charge performance test

A solution containing 0.5 M Li bis(trifluoromethanesulfonyl)imide (LiTFSI; Kishida
Chemical, purity >99.9%), 0.5 M LiNO3 (Sigma-Aldrich, purity >99.9%), and 0.2 M
LiBr (Sigma-Aldrich, purity >99.9%) was used as the electrolyte. LiNO3 and LiBr
were dried at 120 C under vacuum before use. KB-based self-standing carbon mem-
brane without the oxygen treatment with a thickness and carbon loading of 270 mm
and 5.4 mg/cm2 was used for the positive electrode for cell A. KB-based self-stand-
ing carbon membrane without the oxygen treatment with a thickness and carbon
loading of 100 mm and 1.0 mg/cm2 was used for the positive electrode for cell B.
The carbon electrode was dried at 100 C under vacuum for 12 h. Li-O2 cells were
assembled in a dry room with a water content of <10 ppm, by a sequential stacking
of a Li-metal foil (20-mm square, thicknesses of 0.1 and 0.05 mm for cells A and B,
respectively; Honjo Metal), polyolefin-based separator (22-mm square, thickness
of 0.02 mm), porous carbon electrode (20-mm square), and a gas-diffusion layer.
An array of carbon fibers with a diameter of ~10 mm (thickness of 110 mm, TGP-H-
030, Toray) and an array of Ni/Cu-coated polyethylene terephthalate (PET) fibers
with a diameter of ~30 mm (thickness of 45 mm, Sui-40-9027, SEIREN Electronics Ma-
terials) were used for the gas-diffusion layer for cells A and B, respectively. An array
of Ni/Cu-coated PET fibers was also used for the current collector. For cell A, a
ceramic-based solid-state separator (LICGC, thickness of 0.50 mm; Ohara) was
used for the protection of the Li-metal negative electrode. In this case, the
ceramic-based solid-state separator was sandwiched by polyolefin-based separa-
tors, and the same kinds of electrolyte were used for both the positive electrode
side and the negative electrode side. The details of cell configuration were
described in Figure S3. During assembly, 2.5 mL/cm2 of the electrolyte was added
to the separator. A pressure of 100 kPa was applied to the cell by a spring coil.43
Electrochemical experiments were conducted using battery-test equipment (TOS-
CAT, Toyo Systems). For cell A, the limiting capacity and cutoff voltage were set
to 4.0 mAh/cm2 and 2.0 V/4.2 V, respectively. The current density during the dis-
charging and charging process was set to 0.4 and 0.2 mA/cm2, respectively. For
cell B, the limiting capacity and cutoff voltage were set to 3.0 mAh/cm2 and 1.5 V/
4.2 V, respectively. The current density was set to 0.3 mA/cm2.

SUPPLEMENTAL INFORMATION
Supplemental information can be found online at https://doi.org/10.1016/j.xcrp.
2021.100506.

ACKNOWLEDGMENTS
The present work was partially supported by the MEXT (Ministry of Education, Cul-
ture, Sports, Science and Technology) Program for the Development of Environ-
mental Technology using Nanotechnology and the ALCA-SPRING (Advanced Low

10 Cell Reports Physical Science 2, 100506, July 21, 2021

 ll
OPEN ACCESS
Article

Carbon Technology Research and Development Program – Specially Promoted

Research for Innovative Next Generation Batteries, Grant Number JPMJAL1301)
Project of the Japan Science and Technology Agency (JST). A part of this work
was carried out at the NIMS-SoftBank Advanced Technologies Development Center
as a joint research between NIMS and SoftBank Corp. This work also received sup-
port from the National Institute for Materials Science (NIMS) Battery Research
Platform.

AUTHOR CONTRIBUTIONS
S.M. and K.U. conceived the project. E.Y. proposed the initial concept of the self-
standing membrane. S.M., E.Y., and T.K. designed the experiments. E.Y., T.K.,
and S.K. performed the experiments. S.M., S.Y., and Y.K. analyzed the results.
S.M. wrote the paper, with help from all of the authors. S.M. produced all of the
figures.

DECLARATION OF INTERESTS
The authors declare no competing interests.

Received: March 21, 2021

Revised: June 3, 2021
Accepted: June 23, 2021
Published: July 21, 2021

REFERENCES
1. Abraham, K.M., and Jiang, Z. (1996). A Polymer
Electrolyte-Based Rechargeable Lithium/
Oxygen Battery. J. Electrochem. Soc. 143.
https://doi.org/10.1149/1.1836378.
2. Christensen, J., Cook, D., and Albertus, P.
(2013). An Efficient Parallelizable 3D
Thermoelectrochemical Model of a Li-Ion Cell.
J. Electrochem. Soc. 160, A2258–A2267.
3. Kwak, W.J., Rosy, Sharon, D., Xia, C., Kim, H.,
Johnson, L.R., Bruce, P.G., Nazar, L.F., Sun,
Y.K., Frimer, A.A., et al. (2020). Lithium-Oxygen
Batteries and Related Systems: Potential,
Status, and Future. Chem. Rev. 120, 6626–6683.
4. Liu, T., Vivek, J.P., Zhao, E.W., Lei, J., Garcia-
Araez, N., and Grey, C.P. (2020). Current
Challenges and Routes Forward for
Nonaqueous Lithium-Air Batteries. Chem. Rev.
120, 6558–6625.
5. Sakai, K., Iwamura, S., and Mukai, S.R. (2017).
Influence of the Porous Structure of the
Cathode on the Discharge Capacity of Lithium-
Air Batteries. J. Electrochem. Soc. 164, A3075–
A3080.
6. Sakaushi, K., Yang, S.J., Fellinger, T.P., and
Antonietti, M. (2015). Impact of Large-Scale
Meso- and Macropore Structures in
Adenosine-Derived Affordable Noble Carbon
on Efficient Reversible Oxygen Electrocatalytic
Redox Reactions. J. Mater. Chem. A Mater.
Energy Sustain. 3, 11720–11724.
7. Dutta, A., Ito, K., and Kubo, Y. (2019).
Establishing the Criteria and Strategies to
Achieve High Power during Discharge of a Li-
Air Battery. J. Mater. Chem. A Mater. Energy
Sustain. 7, 23199–23207.
8. Mistry, A.N., Cano-Banda, F., Law, D.,
Hernandez-Guerrero, A., and Mukherjee, P.P.
(2019). Non-Equilibrium Thermodynamics in
Electrochemical Complexation of Li-Oxygen
Porous Electrodes. J. Mater. Chem. A Mater.
Energy Sustain. 7, 8882–8888.
9. Olivares-Marı́n, M., Aklalouch, M., and Tonti, D.
(2019). Combined Influence of Meso- and
Macroporosity of Soft-Hard Templated
Carbon Electrodes on the Performance of Li-
O2 Cells with Different Configurations.
Nanomaterials (Basel) 9, 1–13.
10. Shen, C., Xie, J., Liu, T., Zhang, M., Andrei, P.,
Dong, L., Hendrickson, M., Plichta, E.J., and
Zheng, J.P. (2018). Influence of Pore Size on
Discharge Capacity in Li-Air Batteries with
Hierarchically Macroporous Carbon Nanotube
Foams as Cathodes. J. Electrochem. Soc. 165,
A2833–A2839.
11. Xu, S.M., Liang, X., Ren, Z.C., Wang, K.X., and
Chen, J.S. (2018). Free-Standing Air Cathodes
Based on 3D Hierarchically Porous Carbon
Membranes: Kinetic Overpotential of
Continuous Macropores in Li-O2 Batteries.
Angew. Chem. Int. Ed. Engl. 57, 6825–6829.
12. Lyu, Z., Lim, G.J.H., Guo, R., Kou, Z., Wang, T.,
Guan, C., Ding, J., Chen, W., and Wang, J.
(2019). 3D-Printed MOF-Derived Hierarchically
Porous Frameworks for Practical High-Energy
Density Li–O2 Batteries. Adv. Funct. Mater. 29,
1–8.
13. Nomura, A., Ito, K., and Kubo, Y. (2017). CNT
Sheet Air Electrode for the Development of
Ultra-High Cell Capacity in Lithium-Air
Batteries. Sci. Rep. 7, 45596.
14. Park, S.H., Cheon, Y.J., Lee, Y.J., Shin, K.H.,
Hwang, Y.Y., Jeong, Y.S., and Lee, Y.J. (2019).
Maximal Utilization of a High-Loading Cathode
in Li-O2 Batteries: A Double Oxygen Supply
System. ACS Appl. Mater. Interfaces 11, 30872–
30879.
15. Lin, Y., Moitoso, B., Martinez-Martinez, C.,
Walsh, E.D., Lacey, S.D., Kim, J.-W., Dai, L., Hu,
L., and Connell, J.W. (2017). Ultrahigh-Capacity
Lithium-Oxygen Batteries Enabled by Dry-
Pressed Holey Graphene Air Cathodes. Nano
Lett. 17, 3252–3260.
16. Xiao, J., Mei, D., Li, X., Xu, W., Wang, D., Graff,
G.L., Bennett, W.D., Nie, Z., Saraf, L.V., Aksay,
I.A., et al. (2011). Hierarchically porous
graphene as a lithium-air battery electrode.
Nano Lett. 11, 5071–5078.
17. Li, F., Chen, Y., Tang, D.M., Jian, Z., Liu, C.,
Golberg, D., Yamada, A., and Zhou, H. (2014).
Performance-Improved Li-O2 Battery with Ru
Nanoparticles Supported on Binder-Free
Multi-Walled Carbon Nanotube Paper as
Cathode. Energy Environ. Sci. 7, 1648–1652.
18. Lee, Y.J., Park, S.H., Kim, S.H., Ko, Y., Kang, K.,
and Lee, Y.J. (2018). High-Rate and High-Areal-
Capacity Air Cathodes with Enhanced Cycle
Life Based on RuO2/MnO2 Bifunctional
Electrocatalysts Supported on CNT for
Pragmatic Li–O2 Batteries. ACS Catal. 8, 2923–
2934.
19. Li, Y., Li, X., Geng, D., Tang, Y., Li, R., Dodelet,
J.P., Lefèvre, M., and Sun, X. (2013). Carbon
Black Cathodes for Lithium Oxygen Batteries:
Influence of Porosity and Heteroatom-Doping.
Carbon 64, 170–177.
20. Yang, W., Qian, Z., Du, C., Hua, C., Zuo, P.,
Cheng, X., Ma, Y., and Yin, G. (2017).
Hierarchical Ordered Macroporous/Ultrathin
Mesoporous Carbon Architecture: A Promising

Cell Reports Physical Science 2, 100506, July 21, 2021 11

 ll
OPEN ACCESS
Cathode Scaffold with Excellent Rate
Performance for Rechargeable Li-O2 Batteries.
Carbon 118, 139–147.
21. Duan, X., Song, M., Zhang, L., Wang, L., Zhu,
D., and Chen, Y. (2017). Hydroxylated Carbon
Black as Improved Deposition Support for
Discharge Products in Lithium Air(Oxygen)
Batteries. New J. Chem. 41, 12789–12794.
22. Zhang, Y., Zhang, H., Li, J., Wang, M., Nie, H.,
and Zhang, F. (2013). The Use of Mixed Carbon
Materials with Improved Oxygen Transport in a
Lithium-Air Battery. J. Power Sources 240,
390–396.
23. Guo, Z., Zhou, D., Dong, X., Qiu, Z., Wang, Y.,
and Xia, Y. (2013). Ordered hierarchical
mesoporous/macroporous carbon: a high-
performance catalyst for rechargeable Li-O(2)
batteries. Adv. Mater. 25, 5668–5672.
24. Ue, M., Sakaushi, K., and Uosaki, K. (2020). Basic
Knowledge in Battery Research Bridging the
Gap between Academia and Industry. Mater.
Horiz. 7, 1937–1954.
25. Nasybulin, E., Xu, W., Engelhard, M.H., Nie, Z.,
Li, X.S., and Zhang, J.G. (2013). Stability of
Polymer Binders in Li-O2 Batteries. J. Power
Sources 243, 899–907.
26. Guillen, G.R., Pan, Y., Li, M., and Hoek, E.M.V.
(2011). Preparation and Characterization of
Membranes Formed by Nonsolvent Induced
Phase Separation: A Review. Ind. Eng. Chem.
Res. 50, 3798–3817.
27. Xin, X., Ito, K., and Kubo, Y. (2017). Highly
Efficient Br-/NO3- Dual-Anion Electrolyte for
Suppressing Charging Instabilities of Li-O2
Batteries. ACS Appl. Mater. Interfaces 9,
25976–25984.
28. Xin, X., Ito, K., Dutta, A., and Kubo, Y. (2018).
Dendrite-Free Epitaxial Growth of Lithium
Metal during Charging in Li-O2 Batteries.
Angew. Chem. Int. Ed. Engl. 57, 13206–13210.
12 Cell Reports Physical Science 2, 100506, July 21, 2021
29. Chen, J., Chen, C., Huang, T., and Yu, A. (2019).
LiTFSI Concentration Optimization in TEGDME
Solvent for Lithium-Oxygen Batteries. ACS
Omega 4, 20708–20714.
30. Carbone, L., Moro, P.T., Gobet, M., Munoz, S.,
Devany, M., Greenbaum, S.G., and Hassoun, J.
(2018). Enhanced Lithium Oxygen Battery
Using a Glyme Electrolyte and Carbon
Nanotubes. ACS Appl. Mater. Interfaces 10,
16367–16375.
31. Chamaani, A., Safa, M., Chawla, N., Herndon,
M., and El-Zahab, B. (2018). Stabilizing Effect of
Ion Complex Formation in Lithium–Oxygen
Battery Electrolytes. J. Electroanal. Chem.
(Lausanne) 815, 143–150.
32. Wu, C., Li, T., Liao, C., Xu, Q., Cao, Y., Li, L., and
Yang, J. (2017). Enhanced Electrochemical
Performance of Non-Aqueous Li-O 2 Batteries
with Triethylene Glycol Dimethyl Ether-Based
Electrolyte. J. Electrochem. Soc. 164, A1321–
A1327.
33. Augustin, M., Vullum, P.E., Vullum-Bruer, F.,
and Svensson, A.M. (2019). Inside the
Electrode: Looking at Cycling Products in
Li/O2 Batteries. J. Power Sources 414,
130–140.
34. Freunberger, S.A., Chen, Y., Drewett, N.E.,
Hardwick, L.J., Bardé, F., and Bruce, P.G.
(2011). The lithium-oxygen battery with ether-
based electrolytes. Angew. Chem. Int. Ed.
Engl. 50, 8609–8613.
35. Marinaro, M., Theil, S., Jörissen, L., and
Wohlfahrt-Mehrens, M. (2013). New Insights
about the Stability of
Lithiumbis(Trifluoromethane) Sulfonimide-
Tetraglyme as Electrolyte for Li-O2 Batteries.
Electrochim. Acta 108, 795–800.
36. Zhao, Z., Huang, J., and Peng, Z. (2018).
Achilles’ Heel of Lithium-Air Batteries: Lithium
Carbonate. Angew. Chem. Int. Ed. Engl. 57,
3874–3886.
Article
37. McCloskey, B.D., Speidel, A., Scheffler, R.,
Miller, D.C., Viswanathan, V., Hummelshøj, J.S.,
Nørskov, J.K., and Luntz, A.C. (2012). Twin
Problems of Interfacial Carbonate Formation in
Nonaqueous Li-O2 Batteries. J. Phys. Chem.
Lett. 3, 997–1001.
38. Shui, J.L., Okasinski, J.S., Kenesei, P., Dobbs,
H.A., Zhao, D., Almer, J.D., and Liu, D.J. (2013).
Reversibility of anodic lithium in rechargeable
lithium-oxygen batteries. Nat. Commun. 4,
2255.
39. Sun, F., Gao, R., Zhou, D., Osenberg, M., Dong,
K., Kardjilov, N., Hilger, A., Markötter, H.,
Bieker, P.M., Liu, X., and Manke, I. (2019).
Revealing Hidden Facts of Li Anode in Cycled
Lithium–Oxygen Batteries through X-Ray and
Neutron Tomography. ACS Energy Lett. 4,
306–316.
40. Park, J., Kim, M., Kim, J.-H., Choi, K., Lee, H.C.,
Choi, W., Ma, S., and Im, D. (2019). A 1000 Wh
Kg 1 Li–Air Battery: Cell Design and
Performance. J. Power Sources 419, 112–118.
41. Lee, H., Lee, D.J., Kim, M., Kim, H., Cho, Y.S.,
Kwon, H.J., Lee, H.C., Park, C.R., and Im, D.
(2020). High-Energy Density Li-O2 Battery
with a Polymer Electrolyte-Coated CNT
Electrode via the Layer-by-Layer Method.
ACS Appl. Mater. Interfaces 12, 17385–
17395.
42. Zhao, S., Zhang, L., Zhang, G., Sun, H.,
Yang, J., and Lu, S. (2020). Failure Analysis
of Pouch-Type Li–O2 Batteries with Superior
Energy Density. J. Energy Chem. 45, 74–82.
43. Matsuda, S., Yamaguchi, S., Yasukawa, E.,
Asahina, H., Kakuta, H., Otani, H., Kimura, S.,
Kameda, T., Takayanagi, Y., Tajika, A., et al.
(2021). Effect of Electrolyte Filling
Technology on the Performance of Porous
Carbon Electrode-Based Lithium-Oxygen
Batteries. ACS Appl. Energy Mater. 4, 2563–
2569.