Journal of the Korean Physical Society, Vol. 77, No. 11, December 2020, pp.

1035∼1039

Evaluations of Discharge Capacity and Cycle Stability for a Graphene-added

Li1.9 Ni0.35 Mn0.65 O2 Cathode Fabricated by using Carbonate Co-precipitation

Seon-Jin Lee
Department of Polymer Science & Engineering, Korea National University of Transportation, Chungju 27469, Korea

Seong-Jae Kim
Departmeent of Mechanical Engineering, Dong-A University, Busan 49315, Korea

Jong-Tae Son∗
Department of Polymer Science & Engineering, Korea National University of Transportation, Chungju 27469, Korea

(Received 24 February 2020; revised 8 May 2020; accepted 11 May 2020)

Li-rich cathode materials are receiving considerable attention for use inlithium-ion batteries
(LIBs) owing to their high capacity of more 250 mAh/g or higher in the voltage range of 3.0–
4.5 V. However, due to the sharply fading capacity and poor rate-capability of Li-rich cathode
materials, numerous efforts have been made to improve the rate-capability. In this research, Li-rich
Li1.9 Ni0.35 Mn0.65 O2 cathode materials were prepared via a carbonate coprecipitation route, and
graphene, which provides high conductivity and thermal stability, was used during the slurry mix-
ing process. The structures and microstructures of those cathode materials were confirmed using
confirmed usnig X-ray diffraction (XRD) and scanning electron microscopy (SEM). The discharge
capacity and capacity retention were enhanced owing to the high electric conductivity and thermal
stability of graphene.
Keywords: Mn-rich cathode, Carbonate co-precipitation, Graphene
DOI: 10.3938/jkps.77.1035

I. INTRODUCTION trix [15]. In addition, the synthesis conditions are mild

Electric vehicles (EVs) and energy storage systems
(ESSs) need high capacity and power-density lithium-
ion batteries (LIBs) [1,2]. However, the current cathode
materials do not satisfy the demands for higher capacity
and power density [3, 4]. Therefore, the Li-rich layered
cathode materials have become prospective cathode ma-
terials owing to their having a higher capacity of more
250 mAh/g, more reasonable price, and better structural
stability [5–7] than other commercial products. Unfor-
tunately, these complicated materials are difficult to pre-
pare and can exhibit poor rate-capability depending on
the synthesis route.
Nowadays, most precursors are prepared via a copre-
cipitation route as metal hydroxides [8–15]. Unfortu-
nately, the hydroxide coprecipitation route is not easily
controlled for Li-rich materials because Mn(OH)2 easily
oxidizes to MnOOH and Mn3 O4 impurities, leading to
a deviation from the desired stoichiometry. However, a
carbonate coprecipitation method [12–14] is suitable to
synthesize Mn(CO3 ) due to the constant oxidation state
of the transition metal (equal to 2) in the carbonate ma-
∗ E-mail: jt1234@ut.ac.kr
because the pH and atmosphere of reactor can be easily
retained.
Despite the big advantage of their higher capacity,
their poor conductivity is their main drawback, limit-
ing their rate-capability and cyclability. Numerous at-
tempts to improve the rate-capability Li-rich materials
by reducing the particle size, doping with transition met-
als, and adding conductive additives [16–20]. Among
them, the use of reduced graphene oxide (rGO) as a
conductive additive leads to superior rate-capabilities.
However, graphene alone is very rarely applied to Li-rich
cathode materials synthesized by using the carbonate co-
precipitation route. In this paper, we report the addition
of graphene to Li1.9 Ni0.35 Mn0.65 O2 (LMNO) synthesized
via carbonate co-precipitation.
II. EXPERIMENTAL
1. Synthesis of Li1.9 Ni0.35 Co0.65 Mn0.1 O2
[Ni0.35 Mn0.65 ]CO3 powders were prepared via copre-
cipitation. A 1-M aqueous metal solution consisting of

pISSN:0374-4884/eISSN:1976-8524 -1035- 2020

c The Korean Physical Society
-1036- Journal of the Korean Physical Society, Vol. 77, No. 11, December 2020

NiSO4 6H2 O and MnSO4·H2 O was fed into a 4-L contin-

uously stirred tank reactor (CSTR) in an atmosphere
of air. The Na2 CO3 solution and a suitable amount
of NH4 OH solution (chelating agent) were pumped into
the CSTR. The [Ni0.35 Mn0.65 ]CO3 powders made up of
spherical particles were dried at 120 ◦ C for 24 h to re-
move water. The obtained [Ni0.35 Mn0.65 ]CO3 precursor
was thoroughly ground with a suitable amount of Li2 CO3
and calcined at 950 ◦ C for 24 hours in air.

2. Material Characterization

The XRD patterns for the cathodes were obtained us-

ing a Siemens D-5000 diffractometer in the 2θ range from
10◦ to 80◦ with Cu Kα radiation (λ = 1.5406 Å). The
morphology of the obtained powder was observed with
SEM (JSM-7610F, JEOL).

3. Process of Adding Graphene and the Elec- Fig. 1. Illustration of the strategy of this study.
trochemical Test

To prepare the positive electrode, we mixed 0.8 g of

Li1.9 Ni0.35 Mn0.65 O2 powder, 0.1 g of Super-P (Aldrich),
0.9 g of N-methyl-2-pyrrolidone (NMP), 0.1 g of PVDF
(Kureha KF100) binder, and 1 wt% graphene (electrical
conductivity > 103 S/cm, Aldrich, versus the cathode).
After that, the slurry was applied on aluminum (Al) foil
by using a doctor blade to form a film with a thick-
ness of 25 um. The electrode was dried at 120 ◦ C for 4
hours in a vacuum dry oven. The CR2032-type coin cell
was combined in a glovebox using the LNMO cathode
electrode, lithium metal (as anode), porous polypropy-
lene, and a 1-M LiPF6 solution with a 7:3 volume ratio
of dimethyl carbonate (DMC)/ethylene carbonate (EC).
The electrodes were charged and discharged galvanostat-
ically from 2.0 to 4.8 V versus the Li/Li+ at a continuous
current of 17 mAg−1 (0.1 C). The cycle measured were Fig. 2. XRD pattern of the Li1.9 Ni0.35 Mn0.65 O2 .
performed at continuous current density of 170 mAg−1
(1 C).
These peaks may have been caused by Li2 MnO3 . Except
for the peak associated with Li2 MnO3 , the peaks are very
sharp and clear. In addition, the separations between
III. RESULTS AND DISCUSSION the adjacent (006)/(012) and (018)/(110) peaks can be
clearly observed, indicating a typical layered structure.
Figure 1 shows an image of the strategy of this study: Figure 3 shows SEM images of the Li1.9 Ni0.35 Mn0.65 O2
1 production of cheaper, safer, and higher capacity Co- powder. The estimated average particle size ranged from
free Li1.9 Ni0.35 Mn0.65 O2 cathode materials, 2 suppres- 7 to 8 μm, and the secondary particles had a spherical
sion of MnOOH and Mn3 O4 formations by using carbon- morphology, as shown in Figs. 3(a) and (b). The pri-
ate co-precipitation, and  3 enhancement of the electrical mary Li1.9 Ni0.35 Mn0.65 O2 particles had triangular prism
conductivity and the thermal stability of cathode mate- shapes with altitudes from 1.4 to 0.55 nm as shown in
rials by using graphene. Figs. 3(c) and (d).
Figure 2 shows the XRD pattern of LMNO. As can Figure 4 shows the initial charge and discharge curves
be seen, Li1.9 Ni0.35 Mn0.65 O2 exhibits layered character- for the bare and the graphene-added LMNO with a con-
istics, and all peaks, except for two (red dashed circles), stant current density of 17 mA/g (0.1C) cycled in the
can be well indexed to the layered α-NaFeO2 structure. voltage range from 2.0 to 4.8 V. As predicted in Fig. 2,
Evaluations of Discharge Capacity and Cycle Stability for a Graphene-added · · · – Seon-Jin Lee et al. -1037-

Fig. 3. SEM images of the Li1.9 Ni0.35 Mn0.65 O2 particles:

(a) × 5000, (b) × 10,000, (c) × 25,000, and (d) × 50,000.

a high ratio of the electrochemically inactive Li2 MnO3

plateau was clearly observed in the charge curves for all
samples, as shown Fig. 4(a). The dQ/dV plots show
that the exact amounts of Li2 MO3 and LiMO2 can be
calculated through integration, as shown Fig. 4(b). In-
terestingly, as shown Fig. 4(b), both samples failed to
extract all lithium even at a high voltage of 4.8 V. De-
spite the high electrical conductivity of the graphene, the
graphene-added sample caused less delithiation. This
phenomenon is evidence that there was interference with
Fig. 4. (a) Initial charge/discharge curves and (b) corre-
the delithiation. Thus, we had to confirm this phe- sponding dQ/dV plots of the pristine and the graphene-added
nomenon through an additional impedance measure- Li1.9 Ni0.35 Mn0.65 O2 at 0.1 C for voltages between 2.0 V and
ment. The initial discharge capacities of the bare and 4.8 V at 25 ◦ C.
the graphene-added LMNO were 143.2 mAh/g and 191.4
mAh/g, respectively. This enhanced capacity is due to
the high electrical conductivity of graphene. In addition,
with graphene, the columbic efficiency of LMNO was en-
hanced from 52% to 58%. The irreversible capacity of all
electrodes probably resulted from oxygen loss from the
structure in cathode materials and from electrolyte de-
composition during the first cycle above 4.45 V [21,22].
Lee et al. [23] reported that graphene can increase the
thermal stability by suppressing the exothermic reaction
caused by side reactions between the cathode’s active
material and the electrolyte on the surface. Therefore,
the enhanced columbic efficiency suggests that graphene
prevents the loss of oxygen at high voltages.
Figure 5 shows the cycle stability of the pristine and
the graphene-added LMNO electrodes at a current den-
sity of 170 mA/g (1 C) for voltages from 2.0 V to 4.8 Fig. 5. Cyclic performances of the pristine and the
V. The initial discharge capacity of the pristine elec- graphene-added Li1.9 Ni0.35 Mn0.65 O2 at 1 C for voltages be-
trode increased from 123 mAhg−1 to 56.6 mAhg−1 by the tween 2.0 V and 4.8 V at 25 ◦ C.
50th cycle (capacity retention = 46%). The graphene-
added LMNO exhibit an initial discharge capacity of
150.3 mAhg−1 , which decreased to 101.4 mAhg−1 after rial and the electrolyte during cycling was suppressed
the 50th cycle (capacity retention = 67%). This result by the high thermal stability of graphene present on
suggests that the side reaction between the active mate- the surface of the cathode’s active material. Therefore,
-1038- Journal of the Korean Physical Society, Vol. 77, No. 11, December 2020

Fig. 6. Rate performances of the pristine and the

graphene-added Li1.9 Ni0.35 Mn0.65 O2 at 0.1 C and 1 C for
voltages between 2.0 V and 4.8 V at 25 ◦ C.

the improved electrical conductivity and thermal stabil-

ity of the graphene-added Li1.9 Ni0.35 Mn0.65 O2 had dra-
matically enhanced the discharge capacity and the cycle
performance.
Figure 6 shows the rate performances of the pristine
and the graphene-added Li1.9 Ni0.35 Mn0.65 O2 at 0.1 C
and 1 C between 2.0 V and 4.8 V at 25 ◦ C. The rate
performances can be seen to have been improved because
seeing that the discharge capacity that at 1 C increased
more than at 0.1 C. This result is due to the high elec-
trical conductivity of graphene.
Figure 7(a) shows the electrochemical impedance spec- Fig. 7. (a) Impedance plots of pristine and graphene-added
tra for the pristine and the graphene-added LMNO Li1.9 Ni0.35 Mn0.65 O2 before cell test at a state of charge =
materials after 1 cycle. Although graphene had been 0. (b) Lithium diffusion coefficients for the pristine and the
added, the charge-transfer resistance (Rct ) values for graphene-added Li1.9 Ni0.35 Mn0.65 O2 .
these cathode materials increased from 264.8 Ω to 363.4
Ω. Li2 MnO3 is known as an electrochemically inactive
materials. Therefore, as a result of the dQ/dV analysis in (moles/cm−3 ) [24, 25]. The plot of Zre versus the re-
Fig. 4(b) (sky color dashed circle), it is assumed that the ciprocal square root of the lower angular frequencies is
charge transfer resistance is assumed to have increased illustrated in Fig. 7(b). Based on Eq. (2), before the
because the peak area of Li2 MnO3 in the graphene-added cell test, we can calculate the lithium-ion diffusion co-
sample was larger. efficient (DLi ) of graphene-added Li1.9 Ni0.35 Mn0.65 O2 to
EIS can be used to calculate the lithium diffusion co- be 6.87 × 10−16 cm2 /s, which is higher than the value of
efficient (DLi ) by using the following equations: 6.07 × 10−16 cm2 /s for the pristine material. Although
the charge transfer resistance increased, the lithium dif-
Zre = Rct + Rs + σω −0.5 (1) fusion coefficient increased, suggesting that graphene was
coated uniformly, but with pores. This suggested that
the discharge capacity and the rate performance are in-
 2
RT creased.
DLi = 0.5 (2)
AF 2 σW C

where Rct is the charge-transfer resistance, ω the angu-

lar frequency in the low-frequency region, D the diffusion
coefficient, R the gas constant, T the absolute tempera-
ture, F Faraday’s constant, A the area of the electrode
surface, and C the molar concentration of lithium ions
IV. CONCLUSIONS
The Li1.9 Ni0.35 Mn0.65 O2 cathode material was pre-
pared via a carbonate coprecipitation route, and
Evaluations of Discharge Capacity and Cycle Stability for a Graphene-added · · · – Seon-Jin Lee et al.
graphene was used during the slurry mixing process.
The XRD results indicated a well- indexed α-NaFeO2
structure. However, the peak intensity of Li2 MnO3
was slightly larger. The SEM images showed that
the particles sizes in the Li1.9 Ni0.35 Mn0.65 O2 cathode
material ranged from 7 μm to 8 μm and that the
primary particles were triangular-prism-like in shape.
The initial discharge capacities of the pristine and the
graphene-added Li1.9 Ni0.35 Mn0.65 O2 were 143.2 mAh/g
and 191.4 mAh/g, respectively. The cycle stability of
the pristine and the graphene-added LMNO were eval-
uated as 1 C from 2.0 V to 4.8 V at room tempera-
ture. The capacity retentions of the the pristine and
graphene-added Li1.9 Ni0.35 Mn0.65 O2 were 46% to 67%
after the 50th cycle, respectively. The graphene-added
Li1.9 Ni0.35 Mn0.65 O2 had a dramatically improved dis-
charge capacity and cycling stability due to its improved
electrical conductivity and thermal stability.
ACKNOWLEDGMENTS
This study was supported by financial resources
granted by the Ministry of SMEs and Startups, Republic
of Korea (S2928638) and the National Research Founda-
tion of Korea (NRF) funded by the Korea government
(MSIT, No. 2019R1F1A1057220) and by the Technol-
ogy Innovation Program (or Industrial Strategic Tech-
nology Development Program-Material Parts Technol-
ogy Development Project) (20003747, Development of
high-performance cathode material manufacturing tech-
nology through valuable metal upcycling from waste bat-
tery and waste cathode material) funded by the Ministry
of Trade, Industry & Energy (MOTIE, Korea).
-1039-
REFERENCES
[1] M. Armand and J-M.Tarascon, Nature 451, 652 (2008).
[2] B. Dunn, H. Kamath and J-M.Tarascon, Science 334,
928 (2011).
[3] P. G. Bruce, S. A. Freunberger, L. J. Hardwick and J.
M. Tarascon, Nat. Mater. 11, 19 (2011).
[4] M. M. Thackeray, C. Wolverton and E. D. Isaacs, Energy
Environ. Sci. 5, 7854 (2012).
[5] J-H. Kim, C. S. Yoon and Y-K. Sun, J. Electrochem.
Soc. 150, 538 (2003).
[6] C. S. Johnson et al., Electrochem. Commun. 6, 1085
(2004).
[7] T. A. Arunkumar, E. Alvarez and A. Manthiram, J. Elec-
trochem. Soc. 154, 770 (2007).
[8] M. M. Thackeray et al., Electrochem. Commun. 8, 1531
(2006).
[9] Y. Chen et al., Electrochim. Acta 87, 686 (2013).
[10] M-H. Lee, Y-J. Kang, S-T. Myung and Y-K. Sun, Elec-
trochim. Acta 50, 939 (2004).
[11] C. S. Johnson et al., Chem. Mater. 15, 2313 (2003).
[12] X. Q. Liu and Z. M. Guo, Prog. Nat. Sci. Mater. Int. 22,
126 (2012).
[13] J. W. Zhang et al., J. Power Sources 238, 245 (2013).
[14] M. Gao et al., Electrochim. Acta 95, 87 (2013).
[15] S-H. Park et al., J. Power Sources 177, 177 (2008).
[16] M. Konarova and I. Taniguchi, J. Power Sources 195,
3661 (2010).
[17] Y. Ge et al., Electrochim. Acta 55, 5886 (2010).
[18] Y. Yang et al., Electrochem. Commun. 11, 1277 (2009).
[19] X. Li, F. Kang, X. Bai and W. Shen, Electrochem. Com-
mun. 9, 663 (2007).
[20] B. Huang, X. Zheng, D. Jia and M. Lu, Electrochim.
Acta 55, 1227 (2010).
[21] Z. Lu and J. R. Dahn, J. Electrochem. Soc. 149, 815
(2002).
[22] D-K. Lee et al., J. Power Sources 162, 1346 (2006).
[23] J-H. Shim et al., ACS Appl. Mater. Interfaces 9, 18720
(2017).
[24] Y. Zhang, P. Xin and Q. Yao, J. Alloys Compd. 741,
404 (2018).
[25] J. Wang et al., Trans. Nonferrous Met. Soc. China 27,
2239 (2017).