A combined theoretical and experimental approach of a new ternary metal

oxide in molybdate composite for hybrid energy storage capacitors

M. Minakshi1,*, T. Watcharatharapong2, S. Chakraborty2, and R. Ahuja2

1
School of Engineering and Information Technology, Murdoch University, WA 6150,
Australia
2
Department of Physics and Astronomy, Uppsala University, Sweden

Abstract

Sustainable energy sources require efficient energy storage system possessing excellent
electrochemical properties. The better understanding of possible crystal configurations and
the development of a new ternary metal oxide in molybdate composite as an electrode for
hybrid capacitors can lead to efficient energy storage system. Here, we reported a new ternary
metal oxide in molybdate composite [(Mn1/3Co1/3Ni1/3)MoO4] prepared by simple combustion
synthesis with extended voltage window (1.8 V vs. Carbon) resulting in excellent specific
capacity 35 C g-1 (58 F g-1) and energy density (50 Wh Kg-1 at 500 W Kg-1) for a two
electrode system in aqueous NaOH electrolyte. The binding energies measured for Mn, Co,
and Ni 2p are consistent with the literature, and with the metal ions being present as M(II),
implying the oxidation states of the transition metals are unchanged. The experimental
findings are correlated well through density functional theory based electronic structure
calculations. Our reported work on the ternary metal oxide studies (Mn1/3Co1/3Ni1/3)MoO4
suggests that will be an added value to the materials for energy storage.

Keywords: Energy; ternary; molybdate; structural; electronic; electrochemical.

                                                            
E-mail: minakshi@murdoch.edu.au
 

1 
 
 1. Introduction

The energy density of supercapacitors can be improved by increasing the voltage and

capacitance. This can be achieved through selecting the appropriate transition metal cations,

as the energy storage properties are linked to the electrodes and its structure and morphology,

without affecting the cost and safety issues.1 Transition metal cation substitutions such as

cobalt and manganese in oxide framework (MO2) have been extensively studied to increase

the specific capacitance through enhancing the electronic and ionic conduction.2-4 Manganese

oxide is one of the most promising electrode materials with a high specific capacitance of 68

F g-1 examined in three-electrode configuration.5 However, its poor electrical conductivity

and cycling stability have limited its application. Nickel oxide (NiO) materials have

generated great interest due to their low cost, low toxicity, and environmentally friendliness.

Unfortunately, NiO possesses high resistivity, which is a serious setback to apply for a

practical application to supercapacitors.6 Whereas, the phosphate framework (LiMPO4) is

environmentally friendly and have long cycle life with relatively low cost but their low

conductivity limits their energy density and found not suitable for high energy applications.7

Comparing to oxides and phosphate frameworks, metal molybdates (AMoO4; A = Ni,

Co, Mn, etc.) have demonstrated improved electrochemical properties.8-11 Nickel molybdate

(NiMoO4) possessing a redox couple (Ni2+/Ni4+) exhibits a high capacitance, low toxicity and

is cost-effective.12 In the case of cobalt molybdate (CoMoO4) material, preventing a cation

disorder has shown structural preferences along with the rate capability but exhibits lower

capacity and poor cyclability to that of Ni when used in hybrid devices.8-11 In recent years,

mixed metal cations in oxide framework were introduced and found to be more effective for

hybrid supercapacitor electrode in KOH electrolyte than their single layered oxides. 13-14 In an

effort to achieve high performance hybrid supercapacitor, a unique and rationale approach

2 
 
have been developed to a new ternary composite material based on Mn-Co-Ni molybdate

then both the computational and electrochemical results are presented in this work.

To the best of our knowledge, ternary transition metals in metal molybdate have not

been reported yet for hybrid supercapacitor devices. Moreover, in this work, the reported

ternary metal oxide exhibits a wide voltage window that led to improved energy storage

performance. The objective of the current study is the development of a new ternary material

with a different crystal configuration crystallized in the pristine MMoO4 (M = Mn, Co or Ni)

framework and to achieve improved electrochemical performance. The unique role of Co is

to prevent a cation disorder, possessing excellent catalytic characteristics and improving rate
14 13
capability , Mn is believed to support the composite structure and Ni redox couple

contributes obtaining high capacitance 15. The benefits and rationale of choosing each metal

cation in the ternary metal oxide in molybdate have been shown in this work both

computationally and experimentally to improve the electrochemical properties due to the

synergetic effects of multiple cations.

2. Experimental methods

Computational methodology
In order to have a profound understanding of the experimentally synthesized ternary

metal oxide in molybdate systems, the spin-polarized density functional theory (DFT)

calculation is performed as implemented in the Vienna Ab-initio Simulation Package (VASP)

16-17
. The aim is to investigate possible configurations for Mn1/3Co1/3Ni1/3 molybdate termed

as “MCNMoO4” via the geometry optimization, and further study their electronic ground
18
state properties. The projector-augmented wave (PAW) is employed to describe

pseudopotentials of each constituent element with a reasonable energy cut off as 500 eV for

plane wave basis set. The structural relaxation is converged when the total energy of the

configuration is less than 10-5 eV and the Hellmann-Feynman forces are below 0.01 eV/Å.

3 
 
 To evaluate MCNMoO4 structure, the 48-atom NiMoO4 in α- and β-phases are fully

optimized within generalized gradient approximation (GGA) exchange correlation functional

proposed by Perdew, Burke, and Ernzerhof (PBE) 19. Later, they are extended in c-direction

by the repetition of 1×1×3 in order to preserve the desired mixing ratio of transition metal

before used as initial models in sampling procedure. In this process, a generalized special

quasi-random structure (SQS) method 20 in the evolutionary algorithm is employed to explore

the alloy structure as implemented in USPEX. 21 A candidate structure is randomly generated

by applying a permutation operator to one individual. According to our experimental results

of the MCNMoO4 crystallinity, only transition metal atoms are being exchanged under the

permutation. The population size is here designated at 60. In each generation, the structural

order of each candidate is minimized/maximized in order to find the most disordered

/ordered. The selected candidate is thereafter permutated to create a new set of structures for

next generation and these structures will subsequently go through the structural order

optimization. Such procedures are iterated around 30-60 times in each simulation (the

number of generations) and the simulation is repeatedly performed 10 times in this work.

After the sampling process, all obtained structures are fully relaxed using DFT again.

Because of a large system size, the k-point mesh of 1×1×1 is high enough to relatively

compare their computed structures and energetics and will be used in this work. To avoid the

self-interaction error and have a more accurate electronic structure description, HSE06
22-23
functional has been also used with the integration over the Brillouin zone approximated

at Γ point. It is applied in the case of the most stable configuration in each phase. To perceive

the electronic structure of this ternary material, the density of states (DOS) is then

investigated. Since we are not focusing on magnetic property, the only ferromagnetic

configuration is assumedly considered in our calculations.

4 
 
 Synthesis of ternary metal molybdate
MCNMoO4 was synthesized using cobalt, manganese and nickel nitrates in the

presence of ammonium molybdate tetrahydrate and urea as a fuel. All the chemicals were

supplied by Sigma Aldrich. Accurately measured chemicals were dissolved in 20 mL D.I

water and the pH of the solution was adjusted by drop wise addition of ammonia solution.

Subsequently, the solution was evaporated on a heater and moved to an oven with 150oC

temperature overnight. Later, the sample was transferred into a furnace at 300oC for 3 hours.

All the physicochemical characterization of the synthesized ternary metal oxide in molybdate

composite are given in the Figures S1 – S3 and Table S1 of the supplementary material. The

XRD analysis (in Fig. S1) is used to determine the crystal phase of MCNMoO4. The

morphology of the obtained product observed by the TEM images is shown in Fig. S2. X-ray

photoelectron spectra (XPS) acquired from this compound showed  the oxidation states of the

cations present in the ternary composite (Fig. S3) along with the binding energies tabulated in

Table S1.

Electrochemical characterisation of materials

An aqueous solution of 2M NaOH was employed as an electrolyte for all

electrochemical measurements. The hybrid supercapacitor device (shown in Fig. S4) was

constructed with MCNMoO4 as the positive electrode and activated carbon (AC) as the

negative electrode. Galvanostatic charge-discharge experiments and electrochemical

impedance spectroscopy were performed using SP-150, Bio-Logic instrument. Charge–

discharge studies were carried out at a current density of 2 A g-1. Specific capacitance and

energy density of the hybrid device were calculated at the end of each charge-discharge test.

Electrochemical impedance spectroscopy (EIS) was carried out with an amplitude of 5 mV

over a frequency range of 10 MHz to 700 kHz at open circuit potential. The optimal mass

ratio between the two electrodes, AC and CoMoO4, was determined to be 1.6 for the

fabricated asymmetric supercapacitor. Therefore, the mass of the AC (negative) and MMoO4

5 
 
(positive) electrode was 24.0 and 15.0 mg, respectively. The specific capacitance and energy

density of the device have been calculated using the following equations

SC (F g-1) = I ∆t ⁄ m ∆V Eq. (1)

E (W h kg-1) = ½ SC ∆V2 Eq. (2)

where SC is the specific capacitance (F g-1), I is the current (A) imposed to the cell for charge

/ discharge, ∆t is the time taken to discharge in seconds (calculated from the discharge

curves), m is the weight of the active electrodes (CoMoO4 and AC) in g, and ∆V is the

voltage window (V).

3. Results and Discussion

(a) Electronic structure analysis MCNMoO4

3.1. Density Functional Theory (DFT) investigation

The monoclinic structures of α- and β-NiMoO4 in a C2/m space group were optimized

and illustrated in Figure 1a. Basically, their structures look quite similar, but the primary

difference is related to the coordination number of Mo6+ ion and the β angle of unit cells.24

Because of the size and electronegativity of the transition metal (XM) where XMn < XCo < XNi,

the CoMoO4 and NiMoO4 are likely to have more packed structure leading to the formation

of octahedral MoO6 (α-phase) whereas the crystal cell with a higher volume containing

tetrahedral MoO4 (β-phase) is preferable to occur in MnMoO4.24 However, a phase transition

from α- to β-phase was experimentally reported to occur in CoMoO4 and NiMoO4 systems.25

For this reason, the MCNMoO4 ternary composite is possibly formed in either one of them.

According to the sampling results from the evolutionary algorithm, all obtained

structures can be distinguished by the mixing composition of 4 binding octahedral MO6 unit

as shown in Figure 1b. This group of 4 octahedrons is connected by sharing their edges with

each other and all ligands (oxygen) have a bonding with Mo6+ ions. Each 4MO6 unit is

bridged by MoOx components where x = 4 and 6 in α- and β-phases, respectively. Owing to

6 
 
the permutation operator, all binding octahedral units of obtained configurations are

randomly mixed in various types. The representations of a 4MO6 mixing type are here

defined by (n1M1:n2M2:…) where n denotes the number of a center transition atom Mi and

n i  4 . For example, among many possibilities, a 4MO6 unit might be composed of 2

i

different M2+ ions such as 1 octahedral CoO6 connected with 3 octahedral NiO6 or 2

octahedral CoO6 with 2 octahedral NiO6. The former and latter will be then denoted as

(1Co:3Ni) and (2Co:2Ni), respectively.

In Table 1, crystal lattice parameters and total energies of chosen configurations

obtained from PBE and HSE06 based geometric relaxations calculations are reported. It is

noted that the total energy is referenced with that of B1 (ΔE = E - EB1). Moreover, the

structures forming in α- and β-phases are represented as Ai and Bi (where i is a structure

number), respectively, while the BA configuration is originally α-phase structure that

transforms into β-phases after geometry optimization. From the results, the β-phase structure

with a number of diverse 4MO6 units can possibly undergo a phase transformation or even

become an unstable structure. For instance, the B2 configuration which uniformly contains

4MO6 units with (4Mn) and (2Co:2Ni) bases is crystallized in the β-phase. However, the

corresponding geometry of BA is significantly changed to theα-phase with the total energy

increment during the coexistence of (3Co: Ni) and (4Ni) along with (4Mn) and (2Co:2Ni).

This could be attributed to a strong distortion on tetrahedral MoO4 induced by an

inhomogeneous mixing of 4MO6 units. When the MoOx structural unit is too much distorted,

it would lead to a broken confirmation around that particular site.

The stability can be relatively determined from the total energy of structure.

Comparing the total energies of each identical phase structure, we found that A1 and B1

configurations (in Figure 2) prefer to form in MCNMoO4 rather than the one with mixing M

7 
 
in the 4MO6 unit. It is worth mentioning that they both have the identical mixing pattern of

4MO6 unit where only (4M) basis is orderly arranged as depicted in Figure 2. Nevertheless,

B1 is the most stable configuration we have found in this work. The relative energies between

A1 and B1 structures are 0.21 and 1.19 eV based on PBE and HSE06 functional,

respectively. This indicates that when the localization of d-electron is correctly described by

more accurate exchange correlation, the relative stability between α- and β-phases are more

obviously varied in our MCNMoO4 system. Based on the lowest total energy of B1 and B2

configurations, the β-phase structure should highly tend to be observed in MCNMoO4.

A comparative plot of the total energy is depicted in Figure 1c. Here, the relative total

energy is plotted with respect to cell volume and it is noticed that MCNMoO4 structure

becomes more energetically favorable while its cell volume gradually decreases. The

calculated volume per formula (V) of α-NiMoO4 and α-MnMoO4 are shown by dashed-lines

in this plot. One can observe that the volume of ternary metal oxide in molybdate composite

is less than that of α-MnMoO4. This is due to the smaller atomic size as well as the higher X

of Ni and Co atoms. Moreover, it could further imply that a surface area of MCNMoO4

should be relatively higher compared with the pristine α-MnMoO4. Since we know that the

surface area is significantly proportional to the specific capacitance of a supercapacitor, our

results can explain why an initial specific capacitance for the ternary metal oxide in

molybdate is less than Ni-based system but still more as compared to the Mn-based

molybdate as reflected in Figure 4a (discussed in the electrochemical experimental results).

This is also in agreement with the work of Park et al. who found that the surface area of
26
NixCo1-xMoO4 increased with the increase of x Ni content. In one of our earlier works, we

showed that the pristine α-MnMoO4 exhibited a stable electrochemical performance27 as well

as the most stable structure among the group of Mn, Co, and Ni molybdate studied.28

Therefore, the cycling stability of MCNMoO4 system should be undoubtedly improved when

8 
 
it has been crystallized in β-phase. The predictions of ternary metal oxides in molybdate

structure and cycling stability are all in a good agreement with our experimental data,

discussed later in the electrochemical experimental results

The Density of States (DOS) calculations have been performed within PBE and

HSE06 functional. Due to the well-known underestimation of the band gap in PBE,

MCNMoO4 is found to incorrectly show a metallic character. From the HSE06, the predicted

band gap of A1 and B1 configurations are 2.87 and 3.40 eV at Γ point, respectively. Their

projected DOS (PDOS) can be calculated as demonstrated in Figure 3. The electron

contributions of Mo 4d -O 2s hybridization are mostly dominant in the valence band region

between -8 and -4.5 eV, for both A1 and B1. However, in the conduction band, the clear

feature of Mo-O hybridization is observed in a range of 2.2-4 and 5.2-7.3 eV for A1, but

different in a range of 2.9-7 eV for B1. The similarity of their DOS indicates that the

structural phase transformation does not much affect the electronic structure of MCNMoO4.

Additionally, to clearly capture the electron contributions of M, the area under the

corresponding curves are highlighted by the black, blue, and green colors for the PDOS of

Mn, Co, and Ni, respectively. According to crystal field theory, all M2+ ions in two cases are

both found in the high-spin state under the octahedral crystal field of MO6 and they all

undergo the Jahn-Teller distortion. Their electron configuration in d-orbital can be then

  t  e  ,   t   e  ,   e  .
3 3 2 3 2 2 3 2
written as Ni2+: t2g 
2g

g Co2+: t 2g 
2g

g Mn2+: t2g 
g The strong

hybridization of Mn 3d – O 2s obviously shows near the Fermi level (EF), whereas that of Co

3d – O 2s and Ni 3d – O 2s are observed in-depth energy range. In our earlier work on the

pristine molybdate systems, the hybridization of M 3d – O 2p was also observed near the EF,

but the intensity of oxygen part was higher than M, especially for α-phase. It means when an

electron is removed from the bulk MCNMoO4, the redox reaction of M2+ ion would occur

easier in the way that the transition of Mn2+ into Mn3+ is more likely to take place than in the

9 
 
case of other M cations, like Co or Ni. Therefore, we can infer MCNMoO4 has emerged as a

molybdate based new ternary metal oxide system, which could possess improved

electrochemical characteristics to that of pristine counterparts with single metal oxide.

Electrochemical studies have been carried out on this ternary composite electrode to validate

its suitability for energy storage applications.

(b) Experimental analysis of MCNMoO4

3.2 Asymmetric Supercapacitor

In order to explore the practical application of the ternary composite, AC || MCNMoO4

device is fabricated and its sketch is shown in Fig. S4. A potentiostatic (charge-discharge)

experiments have been performed in the device and the results are shown for extended

voltage windows in Figure 4a-b. The symmetrical shape of the charge and discharge curves is

maintained even at a higher voltage window, exhibiting two plateaus in regions 1.4 and 0.5

V, implying the process is reversible. The electrochemical reaction during charge and

discharge constitutes both faradaic (redox reactions observed through discharge plateaus) and

non-faradaic (ion adsorption, a typical capacitive property observed through a quasi-

29-33
triangular shape of curves) processes from the NaOH electrolyte. For the cell tested at

1.4 V cut-off, the coulombic efficiency of the charge to discharge capacitance is found to be

95% (Figure 4b) but this efficiency decreases to 80% for the cell tested at an extended

voltage window 1.85 V. Nevertheless, the available capacitance for the device doubled (~18

to ~ 35 C g-1) for the voltage window from 1.4 to 1.85 V. The specific capacitance for the

various cut-off voltage windows i.e. 1.2, 1.4, 1.6, 1.8 corresponds to 7, 18, 23 and 35 C g-1,

respectively. A discrepancy in coulombic efficiency is due to the ohmic drop of 0.15 V seen

at a higher cut-off voltage window (Figure 4a). Despite this, a large voltage window is of

great importance for practical storage applications and to have larger power and energy

densities. The calculated specific capacitance values at a current density of 0.5, 1, 1.1 and 1.5

10 
 
A g-1 corresponds to 58, 52, 50, and 45 F g-1, respectively. Even at a high current density of

1.5 A g-1, 77% of the capacitance is retained. The decreasing capacitance at a higher current

density is due to low utilization of active materials.

3.3 Long term cycling and EIS analysis

Long term cycling stability of hybrid device (in Figure 4c-d) with a cut-off voltage of

1.85 V was tested over 2000 cycles at a current density of 0.5 A g-1. In comparison to that of

single cation molybdate (Mn, Co, and Ni)28 the available specific capacitance of 58 F g-1 for

ternary (MCNMoO4) composite is higher and found to be quite stable with excellent capacity

retention of 90% at the end of 2000 cycles. The role of Mn cations acts as a stabilizer to

retain the molybdate framework for reversibility and hence the improved capacitance after
27
multiple cycles. The role of Ni and Co enhanced the redox potential and specific
11, 15
capacitance. The presence of nanorods in the composite can provide active sites for

electron transfer to occur and enabling OH- ions access to the structure reversibly that

resulted in enhanced capacitance and retention rate. Among the various criteria to quantify

the performance of a hybrid device, coulombic efficiency is crucial. This indicates the

amount of charge that is involved in a device facilitating an electrochemical reaction. The

ratio of the time taken to discharge and charge the device within the cut-off voltage is defined

as “coulombic efficiency”. The hybrid device (in Figure 4d) with a cut-off voltage of 1.85 V

tested over 2000 cycles showed 80% with an excellent capacitance retention of 90%. The

optimal energy density (E) of the device, using equation (2), is calculated to be 27 Wh Kg-1 at

a power density of 500 W Kg-1, as shown in Ragone plot (in Figure 4e). The obtained energy
8, 11, 15, 29-33
density is superior to those reported in the literature for pristine (single metal

oxide) molybdate as electrodes for supercapacitor applications in the aqueous system. On the

basis of the above discussion, the synergistic effect of three metal oxides and its morphology

through combustion process34 in the molybdate framework paved the way for excellent

11 
 
stability through dynamics of electrons and ions movements within the bulk of the molybdate

particles enhancing the energy density of the ternary molybdate with a wide voltage window.

Electrochemical impedance spectroscopy (EIS) was also conducted and the

corresponding Nyquist plot is shown in Figure 4f. It can be observed that the plot has a very

small semi circle in the high-frequency region and a sloping line in the low-frequency region

indicating a low charge transfer resistance. The Rs value was obtained 4.6 Ω from the

intercept of the Zꞌ axis. The straight line at the lower frequency region is the Warburg

impedance. The deviation of the 90ₒ slope of this line (inset of Fig. 4f) indicates the

pseudocapacitive behavior of the material. 27, 29 The results indicate that MCNMoO4 material

has low internal resistance and small interfacial charge resistance suitable for supercapacitor

properties.

In conclusion, the ternary metal oxide in molybdate composite

[(Mn1/3Co1/3Ni1/3)MoO4] with an appropriate stoichiometric ratio of metal oxide was

successfully synthesized using combustion route. Hybrid supercapacitor was fabricated based

on MCNMoO4 nanorods as a positive electrode and activated carbon (AC) as a negative

electrode in 2M NaOH electrolyte. The ternary composite was found to be crystallized β form

with α-MnMoO4 type in agreement with our density functional theory (DFT) calculations,

revealing the energetically favorable structure. The nanorods possess a specific capacitance

of 58 F g-1 at a current density of 0.5 A g-1 and good reversibility with cycling efficiency of

90% after 2000 cycles. The obtained capacitance is contributed from both electrochemical

double layer capacitance and redox pseudocapacitance that led to high capacitance with

excellent capacitance retention. This new ternary metal oxide in molybdate would be cost

effective with high energy density and high voltage represent major progress towards energy

storage alternatives comparable to that of conventional EDLC and other reported hybrid

capacitors

12 
 
Supplementary material

See supplementary material for the complete physicochemical characterization of

ternary metal oxide in molybdate composite including the schematic diagram of the

supercapacitor device.

Acknowledgments

MM would like to acknowledge the AINSE Research Grant (ALNGRA15051) to carry out

the microscopy work at ANSTO. TW would like to acknowledge DPST administered by

IPST, Thailand. SNIC and HPC2N are also acknowledged for computational supports. SC

and RA would like to acknowledge the Carl Tryggers Stiftelse for Vetenskaplig Forskning

(CTS), Swedish Research Council (VR).

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935-945.
26. K.-S. Park, S. -D. Seo, H.-W. Shim and D. - W. Kim, Electrochemical performance of
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characterization of manganese molybdate for symmetric capacitor applications, Int. J.
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Shafiullah, R.D. Aughterson and R. Ahuja, Effect of transition metal cations on stability
enhancement for molybdate-based hybrid supercapacitor, ACS Applied Mater. Interface
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14 
 
30. X. Mu, Y. Zhang, H. Wang, B. Huang, P. Sun, T. Chen, J. Zhou, E. Xie and Z. Zhang,
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15 
 
Table 1 The geometric details of all optimized Mn1/3Co1/3Ni1/3MoO4 structures calculated
within PBE and HSE06 functionals. The relative total energy (ΔE) is referenced to the total
energy of B1 configuration.
EXC Conf. a (Å) b (Å) c (Å) β (°) V (Å3) ΔE (eV)
A1 9.72 8.85 23.42 114.23 76.55 0.21
A2 9.71 8.85 23.42 114.21 76.51 0.24
A3 9.69 8.84 23.46 114.28 76.34 0.42
PBE A4 9.66 8.83 23.44 114.15 75.95 1.55
B1 10.32 9.36 21.36 106.90 82.25 0.00
B2 10.28 9.34 21.41 106.65 82.05 0.10
BA 9.68 8.83 23.48 114.19 76.22 0.93
HSE06 A1 9.76 8.91 23.22 113.82 76.93 1.19
B1 10.35 9.37 21.30 106.50 82.56 0.00
 

16 
 
 Figure 1 (a) Illustration of permutated structures for ternary metal oxide (Mn1/3Co1/3Ni1/3) in
molybdate composite. (b) A group of 4 binding octahedral MO6 components (M = Mn, Co,
and Ni) in metal molybdate structure. (c) A comparative plot showing a relative total energy
for each considered configurations against their corresponding volumes per formula unit
calculated within PBE functional.

17 
 
 Figure 2 Predicted structures of ternary metal oxide in molybdate composite (a) in α- and
(b) β-phases.

Figure 3 Projected DOS of ternary metal oxide in molybdate composite structures with A1
and B1 configurations. The electron contributions of Mn, Co, Ni, Mo, and O are presented by
black, blue, green, brown, and red lines, respectively. The dashed-line denotes the Fermi
level aligned at 0 eV. 

18 
 
 2.0 60 (b)
(a) 1.85 V

Cell Capacitance / F g-1

rge
Cha Di 50 Charge
Cell Voltage / V 1.5 sc
ha Discharge
rg 40
e
1.0 30

20
0.5
10
1.0 V 1.4 V 1.6 V 1.8 V
0.0 0
0 400 800 1200 1 1.2 1.4 1.6 1.8 1.85
Time / S Charge cut-off voltage / V
          
Specific Capacitance / F g-1

200

Specific capacitance / F g-1

160 (c) MCNMoO4

Coulombic efficiency / %
(d)
100
120 150
80
Ni
80 100 60
MCN
40
40 50
Co 20
Mn
0 0 0
0 500 1000 1500 2000 0 500 1000 1500 2000
Cycle Number / Cycle number /
   

100
80 (e) (f)
Energy density / Wh kg-1

80
Z" / Ohm

60
Range

60
3

40 2
40
Z" / Ohm

20 1

0
20 Acceleration 0 4 5 6
Z' / Ohm
7 8

0 500 1000 1500 2000 0 20 40 60 80 100

Power density / W. Kg-1 Z' / Ohm
 

Figure 4 (a) charge – discharge curves of asymmetric capacitor AC || MCNMoO4 with

different cut-off voltages and (b) bar graph showing the corresponding efficiency between
charge and discharge processes. (c) Long term cyclability of MCNMoO4 in comparison with
MnMoO4,CoMoO4, and CoMoO4. (d) Ragone plot, (e) coulombic efficiency plot and (f)
electrochemical impedance spectroscopy (EIS) analysis of asymmetric capacitor tested at
1.85 V.

19 
 
 2.0 60 (b)
(a)

Cell Capacitance / F g-1

1.85 V
rge
Cha Di 50 Charge
sc
Cell Voltage / V

1.5 ha Discharge
rg 40
e
1.0 30

20
0.5
10
1.0 V 1.4 V 1.6 V 1.8 V
0.0 0
0 400 800 1200 1 1.2 1.4 1.6 1.8 1.85
Time / S Charge cut-off voltage / V

200
Specific capacitance / F g-1
Specific Capacitance / F g-1

160 (c) MCNMoO4

Coulombic efficiency / %
(d)
100
150
120 80
Ni
100 60
80 MCN
40
40 50
Co 20
Mn
0 0 0
0 500 1000 1500 2000 0 500 1000 1500 2000
Cycle Number / Cycle number /

100
(f)
80 (e)
Energy density / Wh kg-1

80
Z" / Ohm

60
Range

60
3

40 2
Z" / Ohm

40
20 1

0
20 Acceleration 0 4 5 6
Z' / Ohm
7 8

0 500 1000 1500 2000 0 20 40 60 80 100

Power density / W. Kg-1 Z' / Ohm