Renewable and Sustainable Energy Reviews 141 (2021) 110798

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

journal homepage: http://www.elsevier.com/locate/rser

Energy storage in metal cobaltite electrodes: Opportunities & challenges in

magnesium cobalt oxide
Syam G. Krishnan a, *, Arunachalam Arulraj a, Mohammad Khalid a, **, M.V. Reddy b,
Rajan Jose c, ***
a
Graphene & Advanced 2D Materials Research Group (GAMRG), School of Engineering and Technology, Sunway University, No.5 Jalan Universiti, Bandar Sunway,
47500, Petaling Jaya, Selangor, Malaysia
b
Hydro-Quebec Institute of Research, CEETSE, Hydro-Quebec, Montreal, Canada
c
Nanostructured Renewable Energy Materials Laboratory, Faculty of Industrial Sciences and Technology, Universiti Malaysia Pahang, 26300, Kuantan, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: Ternary metal cobaltites (TMCs) offering high charge storability, multiple oxidation states, and improved elec­
Pseudocapacitors trical conductivity are widely explored as electrodes for energy storage devices. Among them, magnesium cobalt
Energy storage devices oxide or magnesium cobaltite (MgCo2O4) could be a cheaper analogue due to the abundance of magnesium;
Battery–supercapacitor hybrids
however, limited by materials stability in certain electrolytic conditions, formation of insulating layers hindering
Asymmetric supercapacitors
MgCo2O4
the charge response under charge/discharge conditions. While certain morphologies of MgCo2O4 delivered ca­
pacities higher than the theoretical capacity in lithium ion storage mode, it delivered only a quarter of the
theoretical value in a supercapattery storage mode. This review critically analyzes the progress in MgCo2O4 as a
charge storing electrode for lithium-ion battery, supercapattery (battery-type electrode), and magnesium
rechargeable battery cathodes. A detailed account of the research undertaken is presented herewith and iden­
tifies opportunities and research gaps, which are expected to serve as a guide for future research in ternary metal
cobaltites.

to synthesis low-cost energy storage materials and improve the charge

1. Introduction
Electrical energy storage is accomplished by storing electrical
charges and the mechanism through which they assemble in an elec­
trode and give rise to a voltage distinguish various energy storage pro­
tocols such as batteries, supercapacitors, and pseudocapacitors. One of
the incessant researches on energy storage devices is developing elec­
trode materials characterized by a set of qualities for a particular storage
mode. Therefore, energy storage technology would remain significant
for several upcoming decades. The predicted market of energy storage
materials and devices is worth ~$500 billion by 2025 [1] and that
estimated for electric vehicles is ~$100 million by 2029 [2]. Among the
cost, the electrode materials account for ~40% cost of energy storage
devices [3]. Consumption by this large market often end-up in limitation
of the primary materials supply and to enhance the efficiency of the
energy storage market, cost-effective materials for energy storage ap­
plications are constantly researched [4]. At present, the research intends
storability (energy density) of these devices [5]. Apart from LIBs, re­
searches on materials for other types of secondary batteries such as
magnesium rechargeable batteries (MRBs) [6], sodium batteries [7,8],
aluminum batteries [9,10], lithium sulphur [11,12] and lithium-air
batteries [13,14], electrochemical double-layer capacitors (EDLCs)
and pseudocapacitors [15,16] (together known as supercapacitors
(SCs)) and battery-supercapacitor hybrids (BSHs) [17,18] (also known
as supercapattery (SCAP) or asymmetric supercapacitors (ASCs)) are in
progress. In the latter BSHs, a battery-type electrode (or PCs) occupies
the positive electrode and EDLC occupies the negative electrode and has
been in tremendous attention recently due to their characteristics of
simultaneously high energy density and power density [19,20].
The energy storage materials should offer a range of electrochemical
and surface properties for efficient energy storage [21,22]. Various
materials such as carbons (activated carbon, carbon nanotubes, and
graphene) [23–26], various metal oxides (CuO, MnO2, RuO2, NiO,
Co3O4, and ZnO) [27–31] and their composites (CuO–Co3O4,

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: syamk@sunway.edu.my (S.G. Krishnan), khalids@sunway.edu.my (M. Khalid), rjose@ump.edu.my (R. Jose).

https://doi.org/10.1016/j.rser.2021.110798
Received 25 October 2020; Received in revised form 6 January 2021; Accepted 8 February 2021
Available online 16 February 2021
1364-0321/© 2021 Elsevier Ltd. All rights reserved.
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Abbreviations Ni(OH)2 Nickel hydroxide

Cu(OH)2 Copper hydroxide
SC Supercapacitor Co(OH)2 Cobalt hydroxide
SCAP Supercapattery Zn(OH2 Zinc hydroxide
LIB Lithium ion battery Na2Ti2O4 Sodium titanate
MRB Magnesium rechargeable batteries CuS Copper sulphide
EDL Electric double layer NiS Nickel sulphide
EDLC Electric double layer capacitor MoS2 Molybdenum sulphide
BSH Battery supercapacitor hybrid LiCoO2 Lithium cobalt oxide
ASC Asymmetric supercapacitor LiClO4 Lithium perchlorate
CV Cyclic voltammetry LiBF4 Lithium tetrafluoro borate
CDC Charge discharge cycling LiPF6 Lithium hexafluoro phosphate
EIS Electrical impedance spectroscopy EC Ethylene carbonate
XRD X-ray diffraction DEC Diethyl carbonate
XPS X-ray photoelectron spectroscopy LiC6 Lithium carbide
FESEM Field emission scanning electron microscopy Li4Ti5O12 Lithium titanate
TEM Transmission emission microscopy MgO Magnesium oxide
BET Brunauer–Emmett–Teller NiCo2O4 Nickel cobalt oxide
MOF Metallic organic framework MnCo2O4 Manganese cobalt oxide
SEI Solid electrolyte interphase MgCo2O4 Magnesium cobalt oxide
RHE Reversible hydrogen electrode CuCo2O4 Copper cobalt oxide
TMC Ternary metal cobaltite ZnCo2O4 Zinc cobalt oxide
OSPE Octahedral site preference energy CaCo2O4 Calcium cobalt oxide
FCC Face centred cubic FeCo2O4 Iron cobalt oxide
CuO Copper oxide LiOH Lithium hydroxide
Co3O4 Cobalt oxide KOH Potassium hydroxide
MnO2 Manganese oxide S cm− 1 Seimen per centimeter
RuO2 Ruthenium oxide F g− 1 Farad per gram
NiO Nickel oxide mA h g− 1 milliAmpere hour per gram
ZnO Zinc oxide C g− 1 Farad per gram
TiO2 Titanium oxide eV Electron volt
SnO2 Tin oxide Mg(TFSA)2 Magnesium bis(trifluoromethanesulfonimide)
rGO reduced Graphene oxide PC Pseudocapacitor

NiO–Co3O4, SnO2–Mn3O4, TiO2–SnO2) [32–35]; metal hydroxides (Ni Co content in Co3O4 by developing ternary metal cobalt oxides or co­
(OH)2, Cu(OH)2, Co(OH)2, and Zn(OH)2) [36–39] and hybrid metal baltites (TMCs) or Ternary Transition Metal Oxides (TTMOs) employing
oxide-hydroxides (Na2Ti2O4(OH)2) [40]; chalcogenides (CuS, NiS, Mn2+, Ni2+, Cu2+, Fe2+, Zn2+, and Mg2+ [77]. The synthesized ternary
MoS2) [41,42] and other layered materials (conducting polymers (pol­ metal cobaltites include NiCo2O4 [78], MnCo2O4 [79], MgCo2O4 [80],
yaniline, polypyrrole, indole) [43–45], their composite with metal ox­ CuCo2O4 [81], ZnCo2O4 [82], and CaCo2O4 [83]. Furthermore, these
ides or chalcogenides [46–48]; and metallic organic frameworks (MOFs) TMCs could improve the bandgap or bandwidth of the parent compound
[49–51] are explored as energy storing electrodes. Mostly these elec­ that could enhance the material’s electrochemical activity [84,85]. The
trodes store energy chemically through a range of processes, including oxidation states, electrical conductivity, and the bandgap of various
chemisorption, physisorption, and intercalation. Charge or energy TMCs are compared in Table 1.
storing electrodes, therefore, must comply a range of electrochemical Among these TMCs, magnesium and calcium are largely abundant in
(oxidation/reduction potentials, electrical conductivity, the density of the earth’s crust (2% and 3.5%, respectively); therefore, technological
states, etc.) and surface properties (specific surface area, pore diameter, advancement using these elements would be more sustainable. Despite
and volume, surface energy states of atoms composing materials, etc.) their similar orders of electrical resistivity, the magnesium analogue
[52,53]. Consequently, focus on materials of diverse morphologies such offers a much larger bandgap than the other. Therefore, MgCo2O4 is
as wires, flakes, tubes, flowers, hierarchical structures, etc., are of recently emerging as a potential electrode for electrochemical energy
paramount importance [54,55]. These different morphologies could be storage applications (batteries, supercapacitors) and other miscella­
achieved by adjusting the kinetic parameters such as reaction temper­ neous electrochemical applications such as catalysis [92–97], gas
ature, duration, and precursor volume during synthesis [56,57].
Among the metal oxides, spinal-type cobalt oxide (Co3O4) has
Table 1
attracted a wide range of electrochemical applications such as energy
Oxidation states, electrical conductivity, and bandgap of ternary metal co­
storage [58,59], electrochemical sensing [60,61], and catalytic appli­
baltites for electrochemical applications.
cations [62,63] due to its high theoretical charge storability (~1602 C
Materials Oxidation States Electrical Conductivity Bandgap (eV) Ref.
g− 1), variable oxidation states and improved electrical conductivity [64,
65]. The Co3O4 has been synthesized in a range of morphologies such as Co3O4 +2, +3 ~10–5 1.6–2.10 [86]
nanoparticles [66,67], nanowires [65,68], nanoflowers [69,70], nano­ NiCo2O4 +2, +3 ~10− 4 to 10− 3
2.1–3.6 [87]
MnCo2O4 ~10–4 2.1 [88]
flakes [71,72], and hierarchical structures [73,74] for energy storage
+2, +3
CuCo2O4 +2, +3 ~10–4 2.12–2.15 [89]
applications. However, Co3O4 has certain drawbacks, such as poor CaCo2O4 +2, +3 ~10–4 2.11 [83]
electrical conductivity, toxicity, and rarity [75,76]. In response to the ZnCo2O4 +2, +3 ~10–4 1.71–2.77 [90]
electrical conductivity and rarity, research progressed in reducing the MgCo2O4 +2, +3 ~10–4 ~4 [91]

2
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

sensing performance [98], molecular oxidation of cyclohexane [99], and kg− 1) [110] and are broadly classified into an EDLC and PCs [111]. Most
microwave absorption application [100]. There are several aspects of of the commercial SCs available in the market are EDLCs, where carbons
Mg that favours the replacement of one of the Co atoms in the are used as electrodes and a separator coated with electrolyte [112].
spinal-type Co3O4. In general, magnesium is an alkaline earth metal with During the charge storage process, an electric double layer (EDL) is
zero electron affinity and a stable electronic configuration; comparable formed between electrolyte and electrode layers owing to the static
electronegativity (1.31) similar to Co (1.88) and a common oxidation charge separation thereby preventing the deeper access of the electrode
state of +2 [101]. The ionic radius of Mg (0.72 Å) is comparable to that surface to the solvated ions [113]. However, in PCs materials such as
of Co (+2) (0.65 Å) ions. Besides, Mg is characterized by high negative MnO2, RuOx a faradaic surface redox reaction aids charge storage in
electrode potential (− 2.375V Vs RHE), low cost (<4$ kg− 1), high addition to the EDL [114]. Due to the surface-limited charge intercala­
melting point (649 ◦ C), and low toxicity [102,103]. These characteris­ tion in PC electrodes, their charge reversibility is similar to carbons.
tics would make magnesium compounds sustainable for technological Although these PCs have higher capacitance than EDLC, many factors
applications [104]. hinder their commercialization, including electrolyte dependence,
This article intends to comprehend the energy storage properties of chemical stability of the electrode material, and lower voltage window.
MgCo2O4 towards commercialization and is organized as follows. A brief On the other hand, faradaic charge intercalation extents to the bulk of
discussion on the energy storage parameters of TMCs in general for LIBs the electrode material, thereby offering higher ES in batteries. Numerous
and SCAPs is in the next section (section #2); section #3 details crystal reports show that the positive electrode material tested for LIBs was also
and band structures emphasizing energy storage parameters of MgCo2O4 tested as an electrode material for PC type charge storage in suitable
and LIBs; section #4 briefs the charge storability of MgCo2O4 as a pos­ electrolytes [115,116].
itive electrode material for LIBs; section #5 presents the charge stor­ The practical supercapacitors are typically divided into symmetrical
ability of MgCo2O4 as SCAP electrode considering its composite and supercapacitors or SCs (positive and negative electrodes are usually
addressing the stability issues; section #6 discusses the use of MgCo2O4 ACs) and ASCs or BSHs or SCAPs [117]. The difference in charge storage
as a cathode in MRBs, and finally, our conclusions and recommendations mechanism of SCs and ASCs are schematically shown in Fig. 1. Fig. 1 (a
to improve the charge storability are in section #7 and section #8, & b) show the energy storage process in SCs and its charge storage
respectively. behaviour recorded by cyclic voltammetry (CV); whereas Fig. 1 (c & d) is
similar data of ASCs. Fig. 1 (d) shows that the capacitance obtained from
2. An overview of energy storage parameters of TMCs for SCs, BSH account average capacitance than the instantaneous one showing
SCAPs, and LIBs more battery-type charge behaviour than the PCs [118]. As stated, in
Lithium-ion batteries (LIBs), the faradaic reaction involving lithium ions
Energy storage devices store electrical energy as chemical energy extents to the bulk of electrode materials thereby offering higher charge
through many mechanisms such as breakage of chemical bonds due to storability and ES [119]. The charge movement to the bulk is a slow
the interaction between materials and electrolytes, charge intercalation, process; therefore, LIBs offer much lower PS than SCs and PCs. A similar
and charge adsorption [105–108]. The key performance indicators such schematic highlights the difference in the energy storage process than
as energy density (ES), power density (PS), and cycle life of the SCs, BSHs or SCAPs is drawn for the LIBs and is shown in Fig. 2.
SCAPs, and metal-ion batteries typically LIBs show large variations due The theoretical charge storability of the title compounds, i.e., TMCs,
to the charge storage mechanisms. The fundamental equations in is compared with Co3O4 in Table 3. As mentioned, the question of
determining the ES and PS along with its theoretical capacity and voltage whether an electrode is supercapacitive or not depends on the specific
window are summarized in Table 2. The voltage window is determined electrolyte used; not just on the electrode characteristics alone. There­
for energy storage devices based on the electrolyte selection for the fore, the SCs in Table 3 consider the capacitive storage in the presence of
electrochemical analysis. The voltage window of these devices can vary a suitable electrolyte supporting it; nevertheless, the corresponding
from 0.4 to 3.0 V for aqueous to ionic electrolytes due to the variation of values are converted into units of specific charge for PCs and LIBs.
ionic size in these electrolytes [109]. Therefore, ES, and PS of the device, Among the TMCs, the MnCo2O4 offers larger theoretical charge
vary according to the selection of electrolytes. storability due to the difference in the number of electrons available for
The SCs possess lower ES (~1–15 W h kg− 1) and PS (~1000–5000 W redox reaction (Table 1); Co3O4, and MnCo2O4, involve four electrons,
whereas other TMCs utilize three electrons. Table 3 shows that most of
Table 2 the metal ions which replaced Co2+ ions were transition metal ions
Equations for determining the energy storage parameters of both lithium-ion except MgCo2O4 and CaCo2O4. Mg and Ca are alkaline earth metals;
batteries and supercapacitors. their synergetic combination with metastable Co2O3 is stable with
Factors SCs/PCs SCAP LIB Unit
comparable electrical conductivity, bandwidth, redox state, and theo­
retical capacitances. Further comments on CaCo2O4 do not follow the
Theoretical n×F F⋅g− 1/
CS = Q = C​ = ​ scope of the manuscript. Fig. 3 shows the recent update regarding the
Capacitance/ 3600 × M C⋅g− 1/
Capacity n×F X n×F mA⋅h⋅g− 1 theoretical and achieved capacitance of these ternary metal cobaltites
( ) ( )X
M v M for pseudocapacitor applications. According to Fig. 3, the achieved
Voltage Window − ΔG V
V​ = V​ = V​ = ​ capacitance for NiCo2O4 is higher among these TMCs showing the
n×F
​
− ΔG
​
− ΔG importance of physical properties such as electrical resistance, material
n×F n×F
Energy density C×V W⋅h⋅kg− 1 morphology, and surface properties. As the crystal structure and the
ES ​ = ES ​ = ES ​ = ​
m surface atoms are of paramount importance for a material’s usage as a
1 1 charge storing electrode, the next section details the crystal and band
​ C S V2 ​ QV
2 2
Power density PS ​ = ​ I × V W⋅kg− 1 structure of MgCo2O4.
PS ​ = PS ​ =
ES ES
​
t
​
t 3. Crystal and band structure of MgCo2O4
Note: n, F, M, X, v, ΔG, V and t indicate to the number of electrons (charges) for
SCs and the number of moles of Li ions charge transfer for LIBs, Faraday con­ MgCo2O4 has a spinel structure [120] with a general formula of
stant, molecular weight, duration of redox reaction, redox potential, Gibb’s free AB2O4 (Fig. 4) similar to other TMCs. Fig. 4a depicts the unit cell of
energy, voltage window of the material and time required for the redox process, MgCo2O4, which consists of small interlinked eight face-centred cubic
respectively. For example, the calculated ES of an 18650 LIB cell with a nominal (FCC) units consisting of four A and four B types. The oxygen atom
voltage of 3.6 V, capacity rating of 3.0 Ah and cell weight 45 g, is ~240 Wh/kg. (anion) in MgCo2O4 occupies four effective lattice points of the FCC,

3
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Fig. 1. (a) Schematics of components and working of an SC (b) typical CV curve of a symmetric supercapacitor employing EDLC electrodes (c) schematics of
components and working of an ASC (d) CV curve of a typical ASC/BSH/SCAP using EDLC and battery-type electrodes.

Fig. 2. (a and b) Schematics of components and charge-discharge process in LIBs (c) typical CV curve of a LIB.

making 32 oxygen atoms in the unit cell [121]. There are eight tetra­ half of the four octahedral voids in FCC, contributing to 16 Co atoms
hedral voids per FCC cell and Mg ion occupies 1/8th of such void, thus [122]. Therefore, the unit cell has a formula as Mg8Co16O32; this ion
contributing a total of eight Mg ions in the unit cell. Co atoms occupy distribution is due to octahedral site preference energy (OSPE, defined

4
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Table 3 as the energy difference between octahedral and tetrahedral sites),

Compilation of theoretical capacitance of the TMCs for SC and LIB applications. coulombic interaction between the cations, and radius of cations [123].
Material Theoretical Charge Storability The ions with higher OSPE (Co) occupy octahedral voids and that with
lower energy (Mg) in the tetrahedral voids, thereby forming Co octa­
SCs (F⋅g− 1) PCs (mA⋅h.g− 1) LIB (mA⋅h⋅ g− 1)
hedron and Mg tetrahedron in the MgCo2O4, respectively [85]. The O2−
Co3O4 3560 445 890 coordination further make Mg–O tetrahedron and Co–O octahedron
NiCo2O4 2682 335 891
MnCo2O4 3619 1629 905
vertexes [124]. These cation distributions in the MgCo2O4 crystal
CuCo2O4 2620 453 874 structure is proved by X-ray photoelectron spectroscopy (XPS) [121] and
CaCo2O4 2897 1304 966 Transmission emission microscopy (TEM) [125].
ZnCo2O4 2604 362 975 The distribution of cations in this spinel structure depends on the
MgCo2O4 3122 390 780
experimental conditions (temperature, pressure, and precursors con­
centration) and result in varied morphologies with differing electro­
chemical activities [126]. Fig. 5 shows varied morphologies generated
by controlling the precursor concentration, as reported in our previous
publication [121]. From Fig. 5c, the crystal defects arise from the cation
occupancy, and also the X-ray photoelectron spectroscopy (XPS) data
changes with differing precursor concentration can be observed [101].
However, the cations occupying the tetrahedral and octahedral sites are
stable; therefore, it could be a preferred choice as an energy-storage
electrode [108]. The vacancy sites for ion intercalation in MgCo2O4
for LIBs and MRBs are detailed in recent literature [127]. The reversible
redox reaction of MgCo2O4 for SCAP applications mainly depends on the
electrolyte intercalation to tetrahedral and octahedral sites of the ma­
terials [84]. The electrochemical charge storage in MgCo2O4 in aqueous
electrolytes involves the intercalation of OH− ions explained in equation
(1) [128]. As the equation suggests, the change in Co (Co2+/Co3+)
oxidation states produces a redox reaction in the electrode and the redox
state of Mg (2+) remains unchanged. Also, the formation of the MgO
layer near the electrode-electrolyte surface will be negligible as the
electrode binder shall prevent the large defoliation of Mg to the elec­
trolyte [129]. If a large layer of inert MgO was formed, the SCAP elec­
Fig. 3. Comparison of the theoretical and achieved capacitance of various trode’s cycling stability would have been inferior and not observed in
MCo2O4 nanostructures for supercapacitor applications. the SCAP electrochemical characterization.

Fig. 4. (a) The unit cell structure of MgCo2O4 (b) The cation distribution in MgCo2O4 structure (c) The crystal structure orientation of MgCo2O4 in (111), (311) and
(400) planes; ash and purple polyhedron represent octahedral and tetrahedral sites occupying Co and Mg ions, respectively.

5
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Fig. 5. (I) Comparison of the variation of lattice parameters with Mg content in the lattice in different morphologies (microcrystals, nanoflowers, and nanospheres)
(II) Extended XPS graphs of Mg (1s), Co (2p) and O (1s) of mentioned MgCo2O4 morphologies. Taken with permission from Ref. [121], copyrights 2017, Elsevier
publications.

Charging g− 1) [139] and an intercalated lithiated compound (preferably LiCoO2)

MgCo2 O4 + H2 O + e− ⇄ 2CoOOH + MgO
as a positive electrode [140]. A lithium salt solution such as 1 M LiPF6,
(1)
Discharging
Charging
LiBF4, and LiClO4 dissolved in EC:DEC solution or polymers is used as
2CoOOH + 2H2 O + 2e −
⇄ 2Co(OH)2 + 2OH−
Discharging electrolytes in typical LIBs; electrodes are separated using a permeable
separator allowing Li+ transport [141]. The Li-ion reversible intercala­
MCo2O4 generally possess a spinel structure similar to Co3O4.
tion process in graphite occurs by staging [142,143]. Staging is a ther­
Therefore, under normal circumstances, the substituted cation (M) of
modynamic process involving (i) the energy required by Li+ ions to
Co2+ ions shall occupy tetrahedral sites and Co occupies the octahedral
lower the van der Waal interaction between the adjacent graphite layers
sites [130]. In contrast, if the M atom occupies the octahedral sites and
[144] and (ii) to decrease the repulsive interaction between Li+ ions
Co atoms occupy tetrahedral as well as octahedral sites, an inverse spinel
[145]. Typically, there are four stages, ranging from a dilute stage 4
structure will be formed [131]. It was determined that the free energies
compound to a more concentrated stage-1compound (Fig. 7) [145–147]
of the inverse spinel structure were lower than the normal spinel
following equation (2) proposed by Aurbach et al. for the lithiation of
structure indicating its improved thermodynamics behaviour [85]. The
graphite from diluted stage to stage-1 [148].
projected density of states (PDOS) plot (Fig. 6 (A)) from DFT studies
C6 + 0.083Li+ + 0.083e− ↔ Li0.083 C6 Diluted stage I, LixC6, x ≤
based on the inverse spinel structure of MCo2O4 (M = Mn, Ni, and Cu)
0.083.
show a considerable shift in the valence bands of both the spin to the
Diluted stage I Li0.083 C6 + 0.083e− + 0.083Li+ ↔ Li0.166 C6 stage IV
near Fermi level [85]. This shift reduced the bandgap of Co3O4 from
1.72 eV to 0.35 eV (from G-point of PDOS plot; Fig. 6 (A) for MnCo2O4 tage IV Li0.166 C6 + 0.056 e− + 0.56Li+ ↔ Li0.222 C6 stage III (2)
thereby increasing its electrical conductivity. Similarly, variation in the
Stage III Li0.222 C6 + 0.278 e + 0.278Li ↔ Li0.5 C6 stage II.
− +
insulating nature of Co3O4 to the metallic electronic structure was
observed for CuCo2O4 and NiCo2O4 materials, which could further Stage II Li0.5 C6 + 0.5 e− + 0.5Li+ ↔ Li C6 stage I.
These four stages also follow the pleated-layer model proposed by
enhance its electrochemical properties [85]. Similar results are observed
in other studies for an increase in conductivity with the cation substi­ Daumas and Hérold [149] suggesting a similar amount of Li + ions
distributed among the graphite layers during the intercalation assuming
tution of spinel compounds [84,122,124,132]. To our knowledge, the
band structure of MgCo2O4 is not published so far. no stress involved in the Li+ storage process. However, Raman spec­
troscopy studies of graphite electrodes involving Li+ intercalation pro­
4. Lithium-ion storage in MgCo2O4 cess show local stress along with lattice deformation in graphite
electrode while intercalating from a dilute stage to a concentrated stage
The early years of lithium-ion storage research were on developing [150]. The surface Raman maps as well as the schematics of these stages
of Li+ intercalation in graphite electrode are shown in Fig. 7e. Therefore,
an intercalation cathode whereby various reversible ion, atom, or mo­
lecular intercalation reaction into the host material without disturbing it is advised to charge the commercial LiB between intermediate stages,
avoiding the transition between stage 4 (dilute LixC) to stage 1 (pristine
its crystal structure have been the focus [133]. The general criteria for
the host materials for reversible lithium intercalation reaction are graphite) [150].
Two major issues that hinder the long term cycling of LIBs are
identified as its crystalline nature, empty sites in its crystal lattice, in
addition to its electronic and ionic conductivity [134,135]. This thermal runaway (elevation of temperature at short time interval) [151,
152] and the stability of graphite materials [153,154]; these affect its
reversible lithium intercalation (lithium storage) is facilitated through
several mechanisms such as intercalation reaction, conversion reaction, usage in electric vehicles. Besides, high purity graphite preparation is
cost-intensive [155]; therefore, recent research involved replacing
alloying de-alloying reaction and other possible reactions including
surface charging, free radical mechanism, underpotential deposition, graphite with TMCs. MCo2O4 (M = Ni, Mn, and Zn) were explored as an
anode material for LiBs due to its lower electrical resistance due to its
and interfacial charging [136–138]. Typical LIBs employ graphite as a
negative electrode (despite its lower theoretical capacity of ~372 mA h lower threshold energy for ion transportation compared to binary metal
oxides [156,157]. These MCo2O4 spinel electrodes could facilitate

6
S.G. Krishnan et al.
Fig. 6. The PDOS graphs of the M and Co atoms in MCo2O4 calculated using density functional theory (DFT)+U and its electronic band structures aligning the Fermi
level to 0 eV. Taken with permission from Ref. [85]; copyrights RSC publications.
intercalation of eight Li+ ions (Equation (3)) [158–161] and the mixed
valency state and the semiconductor nature of these materials shall
improve the electrochemical reaction.
MCo2 O4 + 8 Li+ + 8 e− →M + 2Co + 4Li2 O
M + Li2 O ↔ MO + 2Li+ + 2e−
2Co + 2Li2 O ↔ 2CoO + 4Li+ + 4e− (3a)
2 4 4
2CoO + LiO ↔ Co3 O4 + Li+ + e−
3 3 3
Equation (2) provides the advantage and the disadvantage of using
MCo2O4 as a LIB anode. Although the material provides intercalation
sites to eight Li ions, the formation of metal oxides, along with CoO in
the subsequent steps, can reduce the conductivity of MCo2O4 after the
initial charge-discharge process [156]. Furthermore, these irreversible
formations of metal oxide could initiate the volume expansion and the
peeling of anode material after larger charge-discharge cycling [157].
Therefore, a significant result of commercializing these MCo2O4 mate­
rials as an anode material for LIBs is not yet initiated.
7
Renewable and Sustainable Energy Reviews 141 (2021) 110798
The theoretical capacity offered by the MgCo2O4 electrode is ~780
mA h g− 1, more than two times higher than the graphite. The energy
storage mechanism for MgCo2O4 as the LIB electrode involves interca­
lation and conversion reaction and reversible chemical bonding [162,
163]. The lithium-ion intercalation occurs deeper into the electrode
pores employing electrochemical reaction, as shown in equation (3)
[164]. Instead of eight Li+ ions as discussed for other TMCs, six Li+ ions
intercalate into the MgCo2O4 electrode according to equation (3),
thereby having a lower theoretical capacitance than other TMCs.
MgCo2 O4 + 6Li+ + 6e→2Co + MgO + 2Li2 O
2Co + 2Li2 O ↔ CoO + 4Li+ + 4e− (3)
2 2 4 4
2CoO + Li2 O ↔ Co3 O4 + Li+ + e−
3 3 3 3
Metal oxides formed in MgCo2O4 are also similar to other MCo2O4
LIB anodes; therefore, MgCo2O4 is prone to degrading the capacity be­
sides the cycling stability. The amount of MgO evolved in the reaction
determines the reaction’s capacity; the lower the MgO layer formed, the
S.G. Krishnan et al.
Fig. 7. Schematics depicting the alteration of surface equilibrium condition due to Li+ ion intercalation to (a) graphite (b) stage – 4 (c) stage – 3 and (4) stage – 4
showing the volume variation as well as strain between the layers of graphene sheets. (e) Surface Raman maps of pristine graphite electrode and (f) electrode cycled
between 1 and 0.18 V vs Li/Li+ (ID/IG ratio from 48 μm × 74 μm area at ca. 0.7 μm resolution); (e and f) taken with permission from Ref. [150], copyrights 2009,
Elsevier publications.
higher will be the capacitance owing to the improvement of electro­
chemically active sites [165]. Also, solid electrolyte interphase (SEI) is
developed on the anode surface of the LIBs due to side reaction between
lithium electrolyte solvent and salt [164] as given in the below equation
(4).
Li+ + e− + ​ electrolyte ​ →SEI
This SEI, along with the above-mentioned redox reaction involved
with MgCo2O4 are responsible for its cycle life, charge-discharge char­
acteristics, rate capability, and safety. The researches on MgCO2O4 as an
anode material for LIBs was initiated due to two reasons; (i) reducing the
amount of Co in Co3O4 due to environmental and cost issues (ii) the
utility of NiCo2O4, ZnCo2O4, and CuCo2O4 shown improved lithiation
and retention in long term cycling [82,166]. Therefore, it was assumed
that replacing one of the Co atoms with Mg2+ provides an improved
anode material than Co3O4 even though Mg is electrochemically
redundant to Li intercalation. As expected, the initial report of MgCo2O4
as a negative electrode (anode) for LIBs was not very much promising
[80]. As mentioned earlier, its inferior performance has been identified
as the inertness of Mg2+ to Li intercalation as Mg2+ ions cannot be
transformed to MgO due to the higher bond energy of MgO. However,
recent studies determined that the formation of a lower quantity of MgO
layers near the electrode surface shall be reduced by modifying the
anode-electrolyte interface [167]. Therefore, suitable material synthesis
Renewable and Sustainable Energy Reviews 141 (2021) 110798
protocols for developing an electrode of suitable porosity (mesoporous)
and surface area are essential [168] to successfully deploy MgCo2O4 as
anodes for LIBs. The progress in MgCo2O4 research as an electrode
material for LIBs has been summarized in Table 4.
The initial studies on the suitability of MgCo2O4 as an anode material
were explored in 2008 by Sharma et al. [80]. The microneedles of
(4)
MgCo2O4 prepared by an oxalate decomposition technique, however,
performed inferior (736 mA h g− 1 @ 60 mA g− 1) than a benchmark
material FeCo2O4 (827 mA h g− 1) processed under urea combustion
method. The irreversible capacity loss (the difference between charging
and discharging capacitance) after first charge-discharge cycling was
28.4% and 31%, for FeCo2O4 and MgCo2O4, respectively. The proposed
reaction mechanism of lithium intercalation to MgCo2O4 sites included
both the pure and lithium intercalated phases (LiXMgCo2O4). Larger
intercalation of Li to MgCo2O4 lattice shall disintegrate its crystal lattice
resulting in the formation of MgO nanoparticles along with Co and Li2O
formation [80]. Therefore, MgCo2O4 showed higher capacity fading due
to the inert MgO layer formation near the electrode surface; the elec­
trode retained only 0.9 mol of cyclable lithium after 28 cycles of
charge-discharge process. Research for the modification of morphology,
surface area, the porosity of MgCo2O4 as LIB anode, and the techniques
for reducing the formation MgO layer inside it remained idle until 2015.
Researches proved that the transformation to nano-from macro- and
micron-sized materials improved the Li+ intercalation to the vacant
8
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Table 4
Different morphologies and performance of MgCo2O4 as LIB anodes.
Morphology Synthesis Method Capacity (mA⋅h⋅g− 1) @ lower current Capacity (mA⋅h⋅g− 1) @ higher current Cycling stability Ref
density (A⋅g− 1) density (A⋅g− 1)

Microneedles Molten salt method 736 @ 0.06 N.R. ~15% after 60 [80]
cycles
Nanowires Hydrothermal method 940 @ 2.5 550 @ 10 53% after 60 cycles [164]
Nanowires Electrospinning 1576 @ 0.06 411 @ 0.24 ~73% after 60 [169]
cycles
Microparticles Molten salt method 695 @ 0.06 700 @ 0.6 ~109% after 60 [165]
cycles
Hollow Hydrothermal method 1216 @ 0.2 856 @10 ~115% after 100 [170]
microspheres cycles
Porous Hydrothermal method 935 @ 0.5 543 @ 2 ~88% after 150 [171]
nanoparticles cycles
Porous Nanosheets Microwave-assisted liquid phase 1174 @ 0.5 N.R. ~96% after 100 [172]
method cycles
Nanocubes Precipitation method 1384 @ 0.06 886 @ 0.6 ~65% after 50 [173]
cycles

Fig. 8. (a) The X-ray diffraction pattern, (b, c) SEM images and (d, e) TEM image of porous MgCo2O4; (f) HRTEM image; (g) elemental mapping image; (h) EDS
spectrum of as-prepared MgCo2O4 sample. Reproduced with permission from Ref. [171], Copyrights 2019, Elsevier Publications.

9
S.G. Krishnan et al.
material sites, which increases the capacity [174]. In addition to this, the
interconnected structures of nanomaterials such as nanowires, nano­
tubes, and nanosheets could offer improved Li+ transportation, and limit
the volumetric changes during cycling processes [175,176]. Moreover,
tailoring these nanostructures’ porosity enhances the surface area and
the pore size of the material, which further improves the active
electrode-electrolyte interface increasing the lithium charge storage
process [177,178]. Therefore, researches after 2015, focused on devel­
oping nanomaterials with varied morphologies (Table 4) and porosities.
Improvement in capacity to 940 mA h g− 1 at a higher density 2.5 A g− 1
was recorded for MgCo2O4 nanowires grown on nickel foam as a LIB
electrode [164]. The lack of binder in this direct growth method com­
bined with a comparatively higher surface area (45.1 m2 g− 1) improved
Li+ transportation and improved cycling stability (~53%).
Electrospinning method is considered an innovative method for
synthesizing one-dimensional nanomaterials such as nanowires, nano­
belts, and nanoribbons [179]. MgCo2O4 nanowires synthesized using
electrospinning produced an appreciable surface area of 19.2 m2 g− 1 and
delivered a maximum capacity of ~600 mA h g− 1 at 0.24 A g− 1 [169].
This capacity is lower than the nanowires produced by the hydrothermal
method [164]; the binder included for the electrode preparation and its
inferior surface area reduced its capacitance. However, the cycling sta­
bility of the material (~73%) is superior demonstrating lower evolution
of MgO during the cycling process proving the utility of nanowire
morphology. Tailoring the porosity of MgCo2O4 material for improving
the Li intercalation process is gaining momentum recently. Fig. 8 shows
the XRD pattern, FESEM and TEM micrographs, elemental mapping of a
porous MgCo2O4 nanoparticle as an electrode for LIBs [171].
The role of precipitating agents in modifying the porosity of
MgCo2O4 nanocubes was investigated and determined that LiOH is an
Fig. 9. (a) The first three cyclic voltammogram curve of MgCo2O4; (b) The 1st, 5th and 10th discharge–charge curves of the as-synthesized at 100 mA g− 1; (c) Cycling
performances and (d) Rate capability of MgCo2O4 electrode. Reproduced with permission from Ref. [171], Copyrights 2019, Elsevier Publications.
10
Renewable and Sustainable Energy Reviews 141 (2021) 110798
improved precipitating agent than KOH for improved porosity and Li-
ion charge storage [173]. Microspheres with multi shelled porous
structure combined both meso and macropores with an appreciable
surface area (~41 m2 g− 1) provided improved Li+ transportation
channels and intercalation sites [170]. The maximum specific capacity
achieved is 1216 mA h g− 1 at 0.2 A g− 1 higher than its theoretical
capacitance proving a higher amount of Li+ intercalation. The inter­
esting part of the research is the higher cycling stability (~115% after
100 cycles), showing negligible MgO evolution during cycling. Similar
cycling stability (~109% after 60 cycles) could be observed for
MgCo2O4 microparticles [165] synthesized using molten salt method
proving the reduction of MgO layer through proper material synthesis
techniques.
Further research attempts to improve the porosity and the Lithium
storage in MgCo2O4 are still in progress. Recently porous nanoparticles
and nanosheets were synthesized by solvothermal [171] and
microwave-assisted liquid phase method [172]. The SEM micrographs
(Fig. 8b) show the synthesized nanoparticles covered with porous
nanostructures [171] showing improved intercalation sites for Li+
obtaining an appreciable capacity of 935 mA h g− 1 (Fig. 9 a,b) and
~88% of capacitance retention after 150 cycles (Fig. 9 c,d). The assis­
tance of microwave improved the porosity of the MgCo2O4 nanosheets
providing a higher capacity (1174 mA h g− 1 at 0.5 A g− 1) than its
theoretical capacitance and ~96% of capacitance retention after 100
charge-discharge cycles [172].
MgCo2O4 based nanocomposites were also researched to improve
their conductivity, solve SEI problems, and hence the cycling stability.
MgCo2O4/Li4Ti5O12 (LTO) composite was synthesized using a co-
precipitation technique; a two times improvement in the capacity of
pristine LTO was observed [180]. However, the reversible capacity
S.G. Krishnan et al.
achieved was ~300 mA h g− 1 and cycling stability of 85.5% after 150
cycles. The composite’s capacity and stability were lower to other
MgCo2O4 nanostructures, but the activation sites and the conductivity
of LTO improved with MgCo2O4 addition. Recent research modifying
the surface of MgCo2O4 nanorods with TiO2 (MgCo2O4/TiO2 nano­
composite) using oxalate decomposition technique improves the sta­
bility of SEI layer, inhibiting volume difference and further improving
the conductivity along with structural and cycling stability [181]. This
composite provided a maximum reversible capacity of 856 mA h g− 1
with superior cycling stability (~100%) after 300 charge-discharge cy­
cles showing the higher stability of the SEI layer formed on the outer
shell of TiO2. The Li intercalation to the TiO2 layer results in the for­
mation of LiXTiO2, which improves the conductivity and Li+ intercala­
tion [182]. Although these research attempts to lower the MgO layer
formation and increase the Li ion storage in MgCo2O4 are progressing,
the material synthesis techniques discussed in these researches are un­
able to synthesize large-scale MgCo2O4 porous nanostructures replacing
graphite anodes.
Thus, the recent findings on the irreversible MgO formation in the
LIB electrode cites it as an advantage that avoids Mg2+/Mg reaction to
Li+ intercalation [183]. MgO formed during the first charging process
has high dissociation energy, thereby forming an SEI, which further
inhibits any volume variation in the electrode during the electro­
chemical process [164]. Therefore, MgCo2O4 could be utilized as an
anode material solving the bulging thermal away. A research study has
also shown that the calcination temperature plays a crucial role in
obtaining an additional MgO layer in MgCo2O4 that improves the charge
reversibility and capacity retention of LIBs [162]. We note the difference
in these reported capacity values of MgCo2O4 electrodes could be
attributed to the preparation method, morphology, and, most impor­
tantly, normalization of the active material’s weight. Overall irre­
spective of particle size, morphology, and capacity, average discharge
(~1V vs Li) and charge (~2V vs Li) voltage values of MgCo2O4 are
higher than that of other well-known metal oxide anode (Li4Ti5O12)
(1.5V vs Li) [184] and intercalation graphite (0.25V vs Li) [185].
Therefore, future research can improve the voltage hysteresis and the
synthesis of appropriate morphology or composites involving MgCo2O4
using variable synthesizing techniques that emphasize material
scalability.
Fig. 10. Three electrode systems and schematics of the energy storage process in the MgCo2O4 electrode.
11
Renewable and Sustainable Energy Reviews 141 (2021) 110798
5. Charge storability of MgCo2O4 as SCAP electrode
For energy storage applications, light metals from the first four pe­
riods with large capacity are usually preferred [186] and Mg, along with
Co, belongs to a similar category. Various pseudocapacitive charge
storage processes such as underpotential deposition, redox pseudoca­
pacitance, and intercalation pseudocapacitance [111] were involved in
the charge storage materials such as RuO2, MnO2, etc. [187]. The earlier
research reported MgCo2O4 as a pseudocapacitive material citing
intercalation pseudocapacitance [120]. However, its prominent redox
reaction [121] and the asymmetry of the charge-discharge area proved it
to be battery-type or SCAP material.
The material’s SCAP utility is measured using a three-electrode
system as shown in Fig. 10, where the material pasted on nickel foam
or copper foil is measured against a reference electrode (usually Ag/
AgCl) along with the counter electrode (platinum wire). Fig. 10 also
comprises the schematics of the general charge storage process involved
in supercapacitor electrodes. In SCAP, the charge storage process usually
involves redox chemistry of the materials; cation redox reaction causes
energy storage in MgCo2O4 electrodes. The deep intercalation of OH−
ions along with the Mg2+ and Co ions causes redox peaks in CV curves,
demonstrating SCAP behaviour.
The energy storage process of MgCo2O4 as a SCAP electrode
involving cation redox reaction in the aqueous alkaline electrolyte, as
mentioned in Equation (1) [128]. The usual voltage window for the
electrochemical measurements of the MgCo2O4 electrode is from 0 to
0.5 V (for typical alkaline electrolyte). A typical CV curve analyzed by
our research group for the MgCo2O4 electrode is given in Fig. 11; the
redox pairs of Mg/MgO and CoOOH/Co(OH)2 fast reversible faradic
reaction involved in the charge-discharge process can be observed as
redox peaks. There is a change in the valence state of Co2+/Co3+ during
the electrochemical reaction [188]. The CV curve shows asymmetry
between charge-discharge processes showing lower reversibility similar
to batteries signifying it to be a SCAP electrode than a PC one.
Furthermore, the redox peaks in CV curves [120,121] show that deeper
surface intercalation of solvated ions resulting in a difference between
charging and discharging areas providing areal capacitance than specific
capacitance, thereby proving a SCAP charge process. Also, irreversible
surface reaction contributes to SCAP charge storage, enhancing its
asymmetry and increasing the average charge storage.
The basic parameters to be measured in SCAP charge storage pro­
cesses are its reversibility, redox reaction involved, voltage window, the
S.G. Krishnan et al.
Fig. 11. A typical CV curve of MgCo2O4 electrode in the aqueous alkaline
electrolyte at a scan rate of 60 mV s− 1.
practical capacitance, cycling stability, and the resistances (electrolyte,
electrode, and electrode-electrolyte) [188]. The voltage window is the
property associated with the electrolyte and is termed as the potential
window (V) available for the electrochemical process. The capacitance
arises owing to the breaking of the chemical bond between the electrode
materials due to electrolyte ion intercalation and the released energy
(electrical) will be stored as its capacitance [189]. Therefore, the elec­
trode material is equally important as of electrolyte. The energy stored
Fig. 12. (a) Schematics of development of MgCo2O4 nanocones on nickel foam (b) Schematics of MgCo2O4 nanoneedle array development on Ni foam. Taken with
permission from Refs. [128,194], copyrights Elsevier publications (c) Direct growth of MgCo2O4 nanosheets on Ni foam (d) Development of MgCo2O4 nanochain
arrays on Ni foam. With permission from Refs. [195,196], copyrights RSC publications.
12
Renewable and Sustainable Energy Reviews 141 (2021) 110798
in the SCAP electrodes is evaluated by three processes viz. cyclic vol­
tammetry (CV), charge-discharge cycling (CDC), and electrochemical
impedance spectroscopy (EIS) [190]. CV combines the reversibility and
the redox process involved in the charge storage processes, whereas the
CDC measures the device’s practical capacitance. EIS measures the
practical resistances involved in the energy storage processes [191].
Molten salt method was initially used for MgCo2O4 synthesis. How­
ever, lower controllability of the experimental factors such as temper­
ature and duration of the experiment might have hindered its usage
[192]. The MgCo2O4 nano and microstructures were synthesized using
the hydrothermal method for supercapacitor applications [121,188,
193]. The synthesized structures do not have an appreciable surface area
and pore size for achieving higher capacitance values. This may be due
to the surface agglomeration of synthesized materials along with the
binders such as PVDF used for electrode preparation [121,188].
Therefore, the binder-free approach of growing MgCo2O4 nano­
structures on current collectors such as nickel foam using the hydro­
thermal method is gaining popularity among researchers. Fig. 12
compiles the schematics of the hydrothermal synthesis of binder-free
MgCo2O4 electrodes.
The first research attempt at exploring the supercapacitive perfor­
mance of MgCo2O4 was performed by some of us [120], reporting the
cause of CS is intercalation pseudocapacitance. Later, the redox peak in
the CV curves along with the variation in the instantaneous capacitance
in each interval prompted MgCo2O4 prompted researches to classify it as
a SCAP material; the definition of the PC material was misinterpreted as
such in many earlier reports [117]. Therefore, the CS of the MgCo2O4
electrodes as PC electrodes in alkaline electrolytes with clear redox
peaks or non-linear potential decay should be reported in mA⋅h⋅g− 1 or in
C⋅g− 1 than F⋅g− 1. Table 5 comprises the research summary of different
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Table 5
Research summary of MgCo2O4 electrodes analyzed as PC electrodes.
Morphology Method Pore Size distribution (nm) Surface Area Electrolyte CS (F⋅g− 1) CS (mA⋅ h⋅g− 1) Stability Ref
− 1
Microspheres Molten Salt 10.8 0.45 3 M LiOH 320 @ 0.5 A g ~44 100%/3000 [120]
Double urichin Hydrothermal 20–30 26.45 2 M KOH 508 @ 2 A g− 1 ~70 ~96%/2000 [197]
Nanocones Hydrothermal 7.8 335.8 6 M KOH 750 @ 1 A g− 1 ~103 ~84%/1000 [128]
Cuboidal microcrystals Hydrothermal 21 18 3 M LiOH 690 @ 1 A g− 1 ~96 ~106%/3000 [121]
Nanoneedle Arrays Hydrothermal 23.8 25.6 2 M KOH 804 @ 1 A g− 1 ~108 ~87%/2000 [194]
Nanoarrays Hydrothermal N.R. N.R. 6 M KOH 658 @ 1 A g− 1 ~89 ~86%/2000 [198]
Microflowers Hydrothermal 29.6 71.58 2 M KOH 697 @ 1 A g− 1 ~87 ~75%/5000 [193]
Nanoflakes Hydrothermal N.R. N.R. 2 M KOH 530 @ 1 A g− 1 ~74 ~98%/5000 [196]
Nanoflakes Hydrothermal 12.5 64.9 2 M KOH 734 @ 1 A g− 1 ~88 ~94%/5000 [76]
Nanocubes Hydrothermal 9.8 19.6 2 M KOH 541@1 A g− 1 ~65 N.R. [76]
Nanoprisms Hydrothermal N.R. N.R. 3 M KOH – – ~67%/5000 [199]

morphologies, pore sizes of MgCo2O4 as a PC material, and the CS
determined in F⋅g− 1 is converted to mA⋅h⋅g− 1 for future references. From
Table 5, one could observe that most of the recent researches in
MgCo2O4 do not differentiate between PC and SCAP charge storage
proposing the necessity of having a benchmark to differentiate PC and
SCAP electrodes.
Fig. 13 compiles the SEM micrographs or images of these materials.
Morphology of electrode material could positively influence electron
transfer pathways, electrode-electrolyte contact area, and ion diffusion
lengths. The molten salt method was used to synthesize MgCo2O4 mi­
croparticles (Fig. 13a) and explored its utility various electrolytes viz.
neutral and alkaline electrolytes; 3 M LiOH was determined to be the
best performing electrolyte [120]. The ‘V’ for the CD curve was 0.5 V
and the internal resistance of the electrode was also on the lower side
(2.5 Ω). The particle agglomeration of microparticles lowers the BET
surface area (~0.45 m2 g− 1) shall block the electron pathways, thus
lowering the achieved CS signifying the role of morphology in the SCAP
electrode. The increasing CS in cycling stability (from ~80% to ~100%
after 3000 cycles) suggests that the microparticle requires an activation
period to attain its maximum achievable capacitance.
Further, researchers synthesized various morphologies of MgCo2O4
using a hydrothermal method and used them for SCAP applications. The
MgCo2O4 nanoneedle arrays (Fig. 13b) shown an improvement in the
BET surface area (~30 m2 g− 1); electrochemical studies in 2 M KOH
showed an improved voltage window (0.7 V) for CV curve; however, the
CD curve demonstrated a voltage window of 0.5 V [197]. This varied
voltage window for CV and CD curves is due to the potentiostat’s current
rating that depends on the mass loading of electrodes. Therefore, it is
advised to lower the electrodes’ mass loading for potentiostat with lower
ampere ratings to avoid the difference in ‘V’ between CV and CD curves.
The material’s porosity improved its CS owing to lower electrode resis­
tance (~1.5 Ω), showing a CS of ~508 F g− 1 in 2 M KOH at 2 A g− 1.
Direct growth of MgCo2O4 nanocones (Fig. 13c) on nickel foam
provides improved BET surface area (~336 m2 g− 1) proved to be elec­
trochemically active showing a CS of ~750 F g− 1 at 1 A g− 1 in 6 M KOH
[128]. The MgCo2O4 porous nanocones on the nickel foam shorten the
pathways of electrons and electrolyte ions into the electrodes during the
charge-discharge process. However, similar to the earlier reports of
direct grown TMCs on nickel foam [200,201] cycling stability of the
electrode was inferior (~84% after 1000 cycles) at 1 A⋅g− 1 demon­
strating the limitation of the direct growth method for the practical
utility.
The effect of the processing parameters on the morphology (nano­
flowers and cuboidal microcrystals) of MgCo2O4 was studied by our
group following the hydrothermal route [121]. The precursors for both
the morphologies and reaction temperature (100 ◦ C) and duration (12 h)
were the same except the surfactants. Although the BET surface area of
nanoflowers (50 m2 g− 1) was higher than cuboidal microcrystals (18 m2
g− 1) (Fig. 13d), the Mg content in cuboidal microcrystals determined
using Rietveld refinement of XRD was found to be higher. The stacked
morphology could easily facilitate ion transfer, thus showing an
improved CS (690 F g− 1; 96 mA h g− 1) and its cycling stability.
A two-step hydrothermal synthesis and calcination technique suc­
cessfully synthesized MgCo2O4 nanoneedles (Fig. 13e) on nickel foam
[194]. The BET surface area (25.6 m2 g− 1), average pore size diameter
(23.8 nm), and the pore volume (~0.17 cm3 g− 1) were ideal for elec­
trolyte (2 M KOH) ion intercalation. These physical properties of
nanoneedles could produce a maximum CS of 804 F g− 1 and show
appreciable capacitance retention of 87.6% after 2000 cycles. The
electrode resistance of the MgCo2O4 nanoneedles was lower (0.69 Ω)
resulted in improved capacitance of the electrode. The lower resistance
of this electrode could be attributed to the combination of higher active
surface area, higher pore size diameter, and the binder-free electrode
fabrication technique. Although a similar binder-free hydrothermal
fabrication technique is used for the aforementioned MgCo2O4 nano­
cones with higher surface area (336 m2 g− 1) [128], the lower pore size
diameter (7.8 nm) hindered the electrode conductivity lowering its
capacitance and cycling stability. Hence, the electrical conductivity of
the electrode depends on the combination of higher surface, pore size
diameter, morphology, and its redox state.
The porosity of the MgCo2O4 is further optimized using the reaction
time involved in the hydrothermal reaction [193]. The synthesized
micro flower (Fig. 13f) consists of tiny nanosheets whose agglomeration
resulted in the formation of micro flowers further increasing its porosity.
The synthesized micro flowers provided a higher specific surface area
(~72 m2 g− 1) together with pore size distribution ranging from ~21.7
nm to 150 nm; average pore diameter (~30 nm) was superior to other
mentioned morphologies. These conditions would have increased the
contact area between the electrode-electrolyte interface in addition to
the active area utilization. However, the CS of the material was only 697
F g− 1 (~97 mA h g− 1), showing that electrolyte ions do not fully utilize
the porosity, and also cycling stability was on the lower side (74.5%
after 5000 cycles).
Three morphologies: nanosheet, nanobelt, and nanowire arrays
(Fig. 13g) of MgCo2O4, were synthesized by changing the solvent com­
ponents on graphene-coated nickel foam. Nanowire arrays were
showing improved CS of 658 F g− 1 (~89 mA h g− 1) owing to its
improved electron transport channel than the other two morphologies
[198]. The cycling stability of these nanowire electrodes was not
promising (~86% after 2000 cycles), proving the inferior cycling sta­
bility of structures grown on nickel foam; graphene-coated Ni-foam does
not contribute to the stabilization of electrodes.
A comparative study between the various spinel structure, MCo2O4
(M = Co, Mn, Fe, Mg, and Zn) microprisms for SCAP applications,
determined the superiority of MgCo2O4 over other spinels in charge
storage [199]. The MgCo2O4 electrode shown an appreciable areal
capacitance of 613.5 C g− 1 at 2 mA cm− 2. The improved performance is
attributed to the combination of macro and mesoporous nature of the
material, thus lowering the characteristic resistances, which credited to
the enhanced electrode-electrolyte ion transfer.
A recent research attempt synthesized MgCo2O4 nanoflake arrays,
together with MgCo2O4/MgCo2O4 composite hierarchical nanostructure

13
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Fig. 13. SEM images for various morphologies of MgCo2O4 synthesized for SCAP applications. (a)–(g) Taken with permission from Refs. [120,121,128,193,194,197,
198], copy rights Elsevier publications. (h) Taken with permission from Ref. [196], copyrights RSC publications.

14
S.G. Krishnan et al.
(Fig. 13h) [196]. These structures were expected to improve electrical
conductivity, higher redox activity, and higher charge storage proper­
ties. The maximum specific capacitance for nanoflakes and hierarchical
structures was ~317 mA h g− 1 and ~265 mA h g− 1, respectively. The
longer cycling stability of hierarchical structures was promising,
retaining ~98% at 6 A g− 1 after 5000 cycles. The utility of MgCo2O4
nanoflakes with an appreciable mesopore diameter of ~12 nm was
synthesized using hydrothermal synthesis [76]. The porous nature of the
material could explore a maximum capacitance of 734 F g− 1 (~88 mA h
g− 1) and provided a lower resistance (0.75 Ω) to the
electrode-electrolyte ion transfer which increased the achieved CS and
retaining ~95% of CS after 5000 cycles of continuous charge-discharge.
It should be noted that the variation of hydrothermal temperature from
120 ◦ C to 150 ◦ C retaining the similar experimental conditions and
precursors produced nanocubes having inferior pore size (~9.6 nm)
[76] and CS (~65 mA h g− 1). Therefore, the selection of temperature in
the hydrothermal method is important in synthesizing porous
nanostructures.
Fig. 13 and Table 5 suggests that the morphology of the synthesized
nano and microstructures of MgCo2O4 do not provide higher active
surface sites for the electrolyte ion intercalation. The BET surface area
measurements of these materials measure a lower surface area ranging
from 0.45 m2⋅g− 1 to 335.8 m2 g− 1. The extended intercalation (battery-
type) capacitance depends on the pore size distribution and the pore
volume of the electrode materials from Table 5, suggesting that the
different morphologies of MgCo2O4 synthesized for SCAP electrodes
consist of smaller pore size along with lower surface area. The materials’
pore size distribution is also not ideal for the aqueous electrolyte
intercalation for SCAP energy storage as the pore size is much larger
(more mesoporous pores than macropores). The hygroscopic nature of
Mg hinders the broadening of surface ions and the surface agglomera­
tion can be observed from the SEM images in Fig. 12. Also, the elec­
trochemical characterization was performed in alkaline electrolytes and
the cycling stability of the material also needs improvement for material
commercialization. Therefore, future experiments could be designed to
decrease the hygroscopic nature of Mg ions to synthesize 2D layered
structures with higher active surface areas as well as appropriate pore
sizes.
Fig. 14. Schematics of graphene coated MgCo2O4 fabricated on MnO2 core-shell arrays.
15
Renewable and Sustainable Energy Reviews 141 (2021) 110798
5.1. MgCo2O4 composites
MgCo2O4 offers a higher theoretical CS and Table 5 shows that the
maximum achieved CS is ~26% of it. The factors such as lack of elec­
trochemically active sites of the synthesized materials, lower porosity of
materials, and higher electrode resistance might have hindered in
achieving higher capacitance. Therefore, research is focused on com­
posites synthesis or modification of MgCo2O4 for SCAP applications to
improve the stability and the CS.
MgCo2O4 nanoneedles were deposited on silicon carbide flakes
(SiCF) with mesoporous and microporous nature having a higher spe­
cific surface area (1069 m2 g− 1) thereby combining both the EDLC and
SCAP property (MgCo2O4/SiCF nanocomposite) in a single electrode
[202]. This combination has improved the ‘V’ to 0.6 V (1 M KOH) due to
the improvement in the electrochemical active sites as well as the
electrical conducting channels of SiCF. Although there is an increase in
the composite’s surface area, the lower CS proves that the composite has
an increased EDLC behaviour than the battery type charge storage. Also,
this proves that the surface area is not the only criteria to increase the CS
of MgCo2O4; electrochemical characterization resulted in a CS of ~310
C g− 1 or ~71 mA h g− 1 (517 F g− 1) in 1 M KOH at a scan rate of 5 mV s− 1.
The stability of electrodes was promising compared to the pure elec­
trodes (~90% after 5000 cycles), proving that MgCo2O4 composites
could solve the stability issues.
MgCo2O4 nanowires were fabricated at manganese dioxide nano­
flakes core-shell arrays were synthesized on graphene decorated nickel
foam (Fig. 14) and tested its utility for SCAP applications [203].
Although the complex synthesis process involving chemical vapour
deposition and multiple hydrothermal syntheses is noncommercial, the
achieved capacitance is ~887 F g− 1 in 6 M KOH. This improvement
could be attributed to the core-shell arrays for easy electrolytes as well
as electron transfer to the electrode pores. However, similar to the other
direct grown materials on nickel foam, the electrode’s stability was not
promising. It retained only about 87% of its initial capacitance at 10 A
g− 1 at the end of 3000 cycles.
Critical performance analysis of MgCo2O4 as a SCAP electrode shows
two prompt issues with its material synthesis and electrochemical
characterization. The absence of synthesis techniques such as
S.G. Krishnan et al.
electrospinning, microwave-assisted hydrothermal method, etc. hin­
dered the development of porous MgCo2O4 2D, 1D materials with uni­
form surface area and desired porosity. Adopting a suitable ratio of
surfactant to fuel in the hydrothermal method with more optimization in
reaction temperature could develop porous MgCo2O4 for SCAP appli­
cations. Long term cycling or cycling stability was an issue for MgCo2O4
as well as its composites as a SCAP electrode. There are reports of an
increase in capacity even after 3000 CD cycles quoting the structural
activation time as the reason [204]. However, this problem may be due
to the formation of MgO during electrochemical reactions or due to the
dissolution of Mg in the electrolyte solution. Future researches could
explore these problems for the performance stability of MgCo2O4 as an
electrode for SCAP.
5.2. A solution to stability issues
The problem of low cycling stability of MgCo2O4 was investigated by
our research group [188]. Hierarchical MgCo2O4 nanostructures were
synthesized by the hydrothermal method. Its electrochemical studies
determined that the electrodes’ stability issue was caused by the Mg
dissolution from the MgCo2O4 electrode into electrolyte after several
charge-discharge cycles. Reduced graphene oxide (rGO) modified
MgCo2O4 were also synthesized and the electrochemical studies proved
that the Mg dissolution problem decreases with rGO modification of
MgCo2O4 electrodes [188]. A schematic representing the prevention of
electrode material exfoliation owing to rGO modification is shown in
Fig. 15. The variation in the CS cycling stability of MgCo2O4 at intervals
of 5000 charge-discharge cyclings was stabilized using rGO modifica­
tion. Therefore, future research can tailor the quantity of rGO and
compare the stability as well as capacitance improvement in MgCo2O4.
Also, rGO modification could improve the active surface area and the
porosity of MgCo2O4 to achieve a maximum capacitance closer to its
theoretical value.
5.3. Asymmetric supercapacitor (ASC)/battery-supercapacitor hybrid
(BSH)
An asymmetric supercapacitor (ASC) consists of either a pseudoca­
pacitive type/battery type electrode and an EDLC electrode, preferably
activated carbon or mesoporous carbon [205]. The electrodes are
separated by a semi-permeable paper or separator soaked in electrolyte.
Therefore, the ASC combines the properties of both the materials and
expected to combine higher energy density (ES) of the SCAP electrode
Fig. 15. (a) Schematics showing the leaching of MgCo2O4 electrodes in aqueous electrolyte (b) Schematics showing rGO serving as a layer preventing dissolution of
Mg ions to electrolytes (c) Comparison of cycling stability of MgCo2O4 electrodes with rGO modified electrodes, taken with permission from Ref. [188], copyrights
2017, Elsevier publications.
16
Renewable and Sustainable Energy Reviews 141 (2021) 110798
and higher power density (PS) of EDLC materials [206]. The flexible
ASCs will have ionic electrolytes or polymer electrolytes than the
aqueous ones [207,208]. ASCs usually determine the energy and power
density, demonstrating its energy and power capabilities. The ASC
fabrication involving MgCo2O4 as one of the electrode materials is
scarcely reported and most of the research work focuses on the
three-electrode system. The ASCs are fabricated, adopting a charge
balance as q+=q- where q+ and q- are charges of positive and negative
electrodes, respectively [65]. The general equation for a specific charge
stored in both the electrodes is represented by equation (4).
qS = ​ CS × ​ ΔV ​ × ​ m (4)
where the notations have their usual meaning, as discussed earlier. From
the above relation, the corresponding electrode mass requirement for
each electrode can be determined using equation (5)
m− CS+ (SCAP) × ΔV
= (5)
m+ CS− (EDLC) × ΔV
Table 6 compiles the research progress of MgCo2O4 ASCs. An ASC
with MgCo2O4 nanosheets on Nickel foam as a positive electrode and AC
as a negative electrode [195]. 6M KOH is used as an electrolyte for ASCs
whereas 2M KOH for three-electrode studies; the increase in molarity of
KOH could be for a higher voltage window (1.5 V) for the device.
However, the maximum specific charge (Q) in the device at 0.5 A g− 1
was determined to be 52 C g− 1 which is much lower than the Q (947 C
g− 1) of MgCo2O4. Although, the ASC is fabricated calculating the active
area and maximum Q in each electrode; the lower Q of the device shows
that an equal amount of charge transfer between the
electrode-electrolyte interface does not occur [129]. The device’s
maximum energy density was determined to be ~13 W h kg− 1 at a
power density of ~449 W kg− 1, which is comparable with other TMC
ASCs.
Table 6 suggests that maximum research were performed to fabricate
different aqueous ASCs, employing MgCo2O4 as a positive electrode and
AC as a negative electrode with various molar alkaline (KOH and LiOH)
electrolytes. The energy density along with its cycling stability are the
important factors in determining the employability of these devices as a
prototype and a commercial one. In these aqueous ASCs, a maximum ES
of 39.7 W h⋅ kg− 1 is observed with higher cycling stability of 121.1%
after 5000 cycles [199]. A similar increase in capacitance after the
cycling stability test can be observed for the other aqueous ASCs. This
improvement in cycling stability could be attributed to the structural
activation of pores in the electrode material [65]. Usually, metal oxides
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Table 6
Performance summary of ASCs fabricated using MgCo2O4 as positive electrodes.
ASC Max CS Electrolyte Voltage Window (V) ES (W⋅h⋅ kg− 1) @ PS (W⋅kg− 1) Stability (%) Ref

MgCo2O4//AC 52 6 M KOH 1.50 12.99 @ 448.7 80.4 after 2500 cycles [195]
C⋅g− 1
MgCo2O4//AC 76.3 2 M KOH 1.70 30.6 @ 861 99.06% after 5000 cycles [209]
F⋅g− 1
MgCo2O4//SiCF 185.9 C g− 1 PVA-KOH-KI 1.60 41.30 @ 464.7 89.3 after 5000 cycles [210]
MgCo2O4//rGO ~67 PVA-KOH 1.50 81.0 @ 1350 Not Reported [171]
F⋅g− 1
Ni, Zn co-doped MgCO2O4//AC 116.9 F g− 1 3 M KOH 1.70 46.9 @ 132.8 76.4 after 20000 cycles [211]
MgCo2O4//AC 133 3 M LiOH 1.60 31.0 @ 1800 99% after 3000 cycles [129]
C⋅g− 1
MgCo2O4//AC 82.2 F g− 1 2 M KOH 1.70 33.0 @859.6 110.4% after 4000 cycles [76]
MgCo2O4//AC 70.2 F g− 1 2 M KOH 1.70 28.2 @860.4 104.8% after 4000 cycles [76]
MgCo2O4//AC 182.8 C g− 1 3 M KOH 1.60 39.7 @ 396 121.1% after 5000 cycles [199]

provide inferior cycling stability denying their commercialization as
supercapacitor electrodes. The commercially available EDLC has a cycle
life of 103 to 105 cycles and has a higher voltage window of 2.7 V–3.0 V.
Therefore, accepting the commercial capability of these aqueous ASCs is
possible only after a higher number of stability cycles.
For improving the cycling stability as well as voltage window of
aqueous ASCs, Ni and Zn are co-doped with MgCo2O4. However, the ASC
fabricated with the doped MgCo2O4 as cathode and AC as anode showed
improvement in ‘V’ (1.7 V) and ES (46.9 W h⋅ kg− 1), and the cycling
stability of the device was inferior (76.4% after 20,000 cycles) [211].
Similar lower cycling stability was observed for solid-state ASCs
employing PVA-KOH electrolytes [171,210]. In short, ASCs fabricated
using MgCo2O4 as a cathode provided appreciable energy densities
compared to EDLCs. However, these energy densities were not superior
to other TMCs ASCs. Factors such as lower ion transport between the
electrode-electrolyte interface of the device, improper utilization of
active surface area of the cathode and anode could be the reasons for its
inferior performances. Although the charge balance method of mass
loading for cathode and anode assumes an equal amount of charges,
practically the charge balance was not achieved. Therefore, future re­
searches of ASCs employing MgCo2O4 cathodes shall explore these is­
sues to improve their performance.
assumes that the entire electrode mass is electrochemically active for
electron and ion intercalation, which is practically impossible. The
electrode resistance, as well as charge transfer resistance, will be
different for SCAP and EDLC materials. Therefore, the CV curves of these
ASCs show an asymmetry in charge-discharge areas suggesting that the
combination did not utilize the entire mass loading.
Research exploring a trial and error mass loading method compared
to the charge balance method in assembling an aqueous ASC using
MgCo2O4 and AC as electrodes [129]. MnCo2O4//AC were also fabri­
cated as control devices. The research explored fabricating ASCs; ten
ASCs were fabricated varying the positive to negative electrode mass
ratio out of which 1:1 mass ratio gives improved energy density of 31 W
h kg− 1 at a power density of 1.8 kW kg− 1 with 99% of cycling stability
after 3000 cycles at 5 A g− 1. The CV of the device (Fig. 16) with 1:1 mass
loading shows that the asymmetry and the charge storage are improved
than the ASCs fabricated following the charge balance method. This
indicates that further optimization is required in EDLC as well as SCAP
electrodes for ASC fabrication.
5.5. Dependence of electrolyte on the charge storage behaviour of
MgCo2O4

Electrolyte (salt + solvent) contributing ionic conductivity, thereby

5.4. Exploring an alternate way of ASC mass loading
The ASCs were fabricated using a charge balance technique,
assuming that an equal number of charges will be stored in positive and
negative electrodes and a mass balance is required for it (Equation (4)).
Although Equation (4) proves to be theoretically correct, the proper
electrochemical utilization of mass loading is doubtful. This Equation
allowing charge compensation on each electrode in supercapacitors
[213]. The EDL formation for carbon materials and the reversible redox
reactions for SCAP or Battery-type as well as PC materials, will be
influenced by the electrolytes [214]. The factors or characteristics of an
electrolyte such as ion size, solvent-ion interaction, solvent-ion con­
centration (electrolyte molarity), electrolyte-electrode interaction,
voltage window (V) will influence the capacitance of the electrode

Fig. 16. (a) Proposed alternate ASC fabrication method (b) CV of MgCo2O4//AC ASC device for different mass ratios (c) CV of control (MnCo2O4//AC) ASC device
for different mass ratios. With permission from Ref. [129], copyrights 2017, Elsevier publications.

17
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

[109]. The electrochemical influential factors of electrolytes to SCAP Table 7

electrolytes are compiled in Fig. 17. In these factors, ‘V’ influences the Basic Electrolyte properties of different types of electrolytes.
capacitance and working voltage of the SCs, thereby affecting the energy Electrolyte Liquid Electrolytes Solid/semi- Redox
and power density [215]. Also, ion conductivity determines the series Properties solid/gel electrolytes
Aqueous Non-
electrode resistance, which affects the power performance of the device aqueous
electrolytes
[216]. Furthermore, the solvent-ion, along with electrolyte-electrode
Electrical ~0.8 0.006–0.08 ~10–3 ~10–3
interaction, influence the cycle and the shelf life of the SCs [217]. Conductivity
Electrolytes are generally classified into the liquid, solid, or semi- (S cm− 1)
solid and redox-active electrolyte and the broader classification is well Voltage Window ~0.4–~2.0 2.5–2.8 2.5–3.0 0.8–1.0
explained elsewhere [109]. These electrolytes having certain advan­ (V)
tages as well as disadvantages and are well tabulated in Table 7.
Aqueous electrolytes are mostly explored in the electrochemical char­
nature of the synthesized MgCo2O4.
acterization of these MgCo2O4, typically KOH (preferably 6 M) owing to
The compilation of graphs of electrochemical measurements (CV and
its higher conductivity and ion size. However, the electrolyte ion
CD curves) of MgCo2O4 in these mentioned studies gives an insight into
intercalation to the pores of the electrode material rates its charge
the variation of electrochemical properties in different molar LiOH and
storage. Therefore, a varied choice of electrolytes, including aqueous,
KOH electrolytes. Fig. 19 compares the CV, and Fig. 20 compares the CD
solid, or semi-solid besides redox electrolytes will ensure the right
curves of the completed studies. Figs. 19a and 20a compile our SCAP
choice for exploring its maximum theoretical capacitance.
applications in 3 M LiOH [120,121,204]. The CV for lower scan rate (2
Our group initially explored different molar KOH and LiOH elec­
mV s− 1) denotes that the electrochemical characterization of the varied
trolytes and the comparison of the CD curves of these electrolytes at a
MgCo2O4 nano/microstructures differs in redox peaks in the same
similar scan rate is given in Fig. 18a [120]. However, this property may
electrolyte (3 M LiOH). The redox peaks formed in the CV curves are due
vary owing to the porosity of the materials. The electrode’s internal
to the Mg2+ and Co2+/Co3+ intercalation in the pores of the electrode
resistance was higher for 6 M KOH resulted in a huge potential drop
materials and the subsequent reaction is provided in Equation (1). The
compared to 3 M KOH. Furthermore, the CD curves were more sym­
oxidation peak and reduction peak for the MgCO2O4 electrode were
metric for LiOH electrolytes compared to KOH. A closer comparison of
located at ~0.35V and 0.3 V, respectively in 3 M LiOH from the CV curve
the CV curves of MgCo2O4 electrodes in 3M LiOH and 3 M KOH, con­
(Fig. 18b). A variation in the oxidation and reduction peak position
firms the change of redox potential of the same material in different
concerning 3 M KOH is observed from Fig. 18b. Similarly, the change in
electrolytes. The potential (V) above 0.5 V in 3 M KOH is comprised of
oxidation and reduction potential for various MgCo2O4 morphologies in
the decomposition of water and is shown in Fig. 18b. Therefore, re­
3 M LiOH is shown in the CV curves (Fig. 19 a.) This suggests that the
searchers should critically select the electrolytes depending on the

Fig. 17. Schematic showing the SCAP properties depending on electrolytes.

18
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Fig. 18. Comparison of CD curves of MgCo2O4 electrodes in various molar aqueous electrolytes.

Fig. 19. CV curves of different morphologies of MgCo2O4, (a) microstructure, cuboidal microcrystals, and hierarchical structures (b) nanocones (c) double urchin
like hierarchical structures (d) Nanowires in aqueous electrolytes. Taken with permission from Refs. [121,128,197,198], copyrights 2017, Elsevier publications.

redox peaks of MgCo2O4 depend on both the morphology and electro­
lytes used for electrochemical characterization.
Besides, the H2/O2 evolution has occurred for microparticles in the
voltage range of ~0.45 V, whereas the hierarchical structures do not
show this water decomposition of 3 M LiOH. The redox peaks seem to be
merged for the other CV curves, indicating ion intercalation variation to
the electrode surface. Similarly, the CD curve also shows a variation in
potential drop (ΔV) for different structures proving the variation of
resistance to electrolyte ions. Also, MgCo2O4 nanostructures mentioned
in Table 4 use KOH (2 M and 6 M) for the electrochemical character­
ization. The variation in the energy storage process could be observed
from the CV and CD graphs (Fig. 19b–d, Fig. 20b–d).
SCAP charge storage studies of MgCo2O4 is limited to two aqueous
electrolytes, typically LiOH and KOH. However, the interaction between
electrode-electrolyte ions determines the intercalation mechanism of the
electrode materials. Apart from this, the unsolved ionic size also affects
the SCAP charge storage. Researches prove that the charge storage
mechanism of MnO2 improved with LiOH as an electrolyte than KOH
and citing the reason to be the small ionic radius of Li+ than K+ for easy
intercalation [218]. Similarly, reports of an increase in charge storage
are reported for NiO electrodes using NaOH electrolyte than KOH due to
the higher intercalation rate of Na+ than K+ [219]. Matching of pore
sizes of electrode material and electrolyte ions may improve the inter­
calation reaction, thereby improving the charge storage. Therefore,
exploring various electrolytes matching the pore sizes of different
morphologies of MgCo2O4 as a SCAP electrode shall improve its

19
S.G. Krishnan et al.
Fig. 20. The GCD curves of different MgCo2O4 morphologies, (a) microstructure, cuboidal microcrystals, and hierarchical structures (b) nanocones (c) double urchin
like hierarchical structures (d) Nanowires in aqueous electrolytes. Taken with permission from Refs. [121,128,197,198], copyrights 2017, Elsevier publications.
practical energy storage capability.
6. MgCo2O4 as a cathode in magnesium rechargeable batteries
(MRBs)
The main disadvantage of LIBs is the safe deployment of metallic Li
as an anode (negative electrode) due to the thermal runaway of Li after
several cycles of charge-discharge [220]. Replacement of metallic Li
with graphite, a material that can absorb Li+ ions at similar potential,
results in a 10-fold decrease in the energy density of LIB [221]. Research
on stabilization of Li metal anode developing suitable electrolyte addi­
tives such as chlorosilanes, chloroboranes, and chlorophosphines enable
a protective layer of Li surface to decrease thermal runaway is also in
progress [222]. The limited availability of lithium to certain countries
such as Australia, Chile, and Argentina, especially in 0.04–1.16% in
brine ponds, and its longer duration for the synthesis of lithium car­
bonate (~1 year) results in its increased cost [183]. Therefore, research
progressed further to determine alternate elements to replace lithium.
Sodium-ion batteries (SIBs) are one such investigated energy storage
devices replacing Li with Na [223]; however, a thermal runaway
behaviour similar to LIB was also reported on SIB.
Metallic Magnesium (Mg) demonstrated desirable electrochemical
properties such as lower redox potential and lower reactivity (flamma­
bility), thereby presenting as a candid anode material replacing Li metal
to form MRBs [224]. Furthermore, the earlier mentioned properties of
Mg, such as low cost and higher relative abundance, increase its
advantage as an anode of the energy storage device. Also, the high
gravimetric (2205 mA h g− 1) and volumetric (3833 mA h cm− 3)
capacitance of Mg compared to Li presenting its more suitability in
portable electronic devices such as mobile phones over LIBs and NIBs
[225]. The lower standard electrode potential of Mg (− 2.4 V vs SHE)
along with the higher ionic radius of Mg2+ ions shall enable faster ion
20
Renewable and Sustainable Energy Reviews 141 (2021) 110798
diffusion in cathodes. Although, with all these advantages, the two main
hindrances for MRB research are the synthesis of suitable cathode ma­
terial for Mg2+ ion intercalation and the design of an appropriate elec­
trolyte system [225]. Mg insertion demands a combination of high
electromotive force as well as high cation mobility for the cathode
material [6,226]. Although oxide materials provide high electromotive
force, their higher activation energy of diffusion lowers the cation
mobility [227]. However, this section is not exploring the cathode
(positive electrode) and electrolyte materials for MRBs but is limited to
the recent research prospects on developing MgCo2O4 as an MRB
cathode.
The utility of MgCo2O4 synthesized using a reverse co-precipitation
technique as a cathode for MIB is tested with Mg as an anode and Mg
(ClO4)2 as electrolyte [104]. The study assumed equation (6) for Mg2+
intercalation.
Mg1− x Co2 O4 + yMg2+ + 2ye →Mg1− (6)
x+y Co2 O4
yMg → yMg2+ + 2ye
where x determines the number of earlier charges and y determines the
number of discharge charges. This study presented the advantage of
spinel MgCo2O4 for Mg2+ ion intercalation with a voltage window of 3.5
V lighting a blue LED with a bandgap of 2.6 V. However, the solid-state
diffusion process of Mg2+ions was lower, providing a lower energy
density. Okamato et al. further validate the utility of MgCo2O4 as an
electrode for MRBs, suggesting vacant 16c sites on which Mg cations can
be inserted, as shown in Fig. 21a [127]. Fig. 21b shows the significance
of MgCo2O4 as a cathode for MRBs, showing its charge-discharge
capability at 1/10 C, showing a higher working potential after the 1st
discharge process (2–2.5 V vs Mg/Mg2+).
Additionally, the study has demonstrated that the MRBs prepared
S.G. Krishnan et al. Renewable and Sustainable Energy Reviews 141 (2021) 110798

Fig. 21. (a) Schematic illustration of the Mg cation insertion process in vacant 16c sites (b) Cathode performance test at 1/10 C for MgCo2O4 electrode. Taken with
permission from Ref. [127].

using MgCo2O4 works at higher temperatures (~150 ◦ C) and Mg
insertion occurs at the higher potential of 2.9 V Vs Mg2+/Mg with the
change in the valence state of Co(III) to Co(II) (Fig. 22a and b). Also, the
study reveals that Mg insertion and extraction become more accessible
at elevated temperatures. This reaction mechanism is further studied
using XANES (X-ray absorption near edge spectroscopy). The XRD pro­
file after the discharge of 120 mA h g− 1 shows the presence of two both
Fig. 22c reveal the formation of spinel and rocksalt single phase and
further insertion of Mg up to 210 mA h g− 1 transform it to single rocksalt
phase. The XANES profile (Fig. 22 d) proves the reversible redox reac­
tion of Co (III) cations in the spinel phase to Co (II) during the charge-
discharge process at 120 mA h g− 1.
Sa et al. [167] further studied the Mg-intercalation mechanisms and
the electrode-electrolyte interface of an MRB cell using

Fig. 22. (a) CV curve of MgCo2O4 electrode at 150 ◦ C (b) Comparison of lower CV curves of MgCo2O4 in ionic electrolytes at room temperature and 100 ◦ C (c)
comparison of XRD profile of MgCo2O4 with raw one and after the charge-discharge process (d) XANES spectra for synthesized MgCo2O4 and electrode during charge-
discharge process. Taken with permission from reference [127].

21
S.G. Krishnan et al.
scanning/transmission electron microscopy (S/TEM) to detect the
presence of amorphous MgO with crystalline MgCo2O4 materials, pre­
venting its long-term cycling. An intercalation-initiated surface con­
version pathway is suggested for reducing amorphous MgO in the
interface. First-principle calculations were also made in substituting Mn
in MgCo2O4 (MgCo1.5Mn0.5O4) for its utility as MRB cathode; the
calculation and experiment prove that improved Mg insertion in
MgCo1.5Mn0.5O4 owing to weaker Mg–O bonds near Mn [228]. There­
fore, selecting a suitable transition metal and substituting it in MgCo2O4
may improve the cycling stability of MgCo2O4 as a cathode for MRBs.
The transformation of spinel structure to rock salt structure of
MgCo2O4 is validated using electron radiation from a scanning trans­
mission electron microscopy (S/TEM) [229]. These experiments, along
with first-order calculation, prove that the proposed intercalation-push
out process of Mg ions into MgCo2O4 could be its reaction mechanism
of energy storage as MIB cathode. The schematics, along with SRTEM
images of this crystal structure transformation is given in Fig. 23. It was
determined that there is a small energy difference (39 meV) between the
Mg ions located at 8a sites and 16c sites owing to the transformation of
spinel to rock salt structure.
The elevated temperature utility of MRB could facilitate improved
intercalation of Mg2+ ions to the cathode material [127,230,231].
Moreover, Mg(TFSA)2 based electrolytes where TFSA stands for bis
(trifluoromethanesulfonyl) could give appreciable cycling stability and
charge storage at higher temperatures [232,233]. Nevertheless, the
passivation of Mg- metal anode owing to the TFSA decomposition
Fig. 23. S/TEM images of MgCo2O4 structures and their transformation owing to the electron radiation. With permission from Ref. [229], copyrights 2019, Elsevier.
22
Renewable and Sustainable Energy Reviews 141 (2021) 110798
resulting in a large overpotential for Mg dissolution [234–236]. Lately,
the modification of this electrolyte (Mg(TFSA)2) with MgCl2/triglyme
(G3) could suppress the overpotential of Mg dissolution, hence inhibit­
ing the passivation of Mg metal [237]. Further research on improving
the intercalation sites of Mg2+ in the MgCo2O4 spinel structure and
reducing the MgO formation in the electrode-electrolyte interface shall
contribute to developing a commercial MIB.
7. Conclusions
Thus, MgCo2O4 is a material with promising electrochemical prop­
erties such as high theoretical charge storability, availability of a range
of charge intercalation sites and oxidation states, and comparable
electrical conductivity with many other electrochemical materials, for
its potential deployment in energy storage devices. However, there are
serious drawbacks, such as material stability under certain electrolytic
conditions, formation of the inert layer during charge-discharge cycling,
knowledge-gap on the materials’ physics, and cobalt oxide rarity. Our
analysis shows that several studies have been reported on the processing
– property correlation with MgCo2O4 with a focus on developing diverse
morphologies and their property evaluation for lithium ion batteries,
battery-supercapacitor hybrids, and magnesium ion batteries. Among
the only seven MgCo2O4 morphologies reported so far as a lithium ion
battery electrode, few of them report higher lithium discharge capacity
in the MgCo2O4 electrodes than the theoretical prediction. This provides
ample opportunities to explore this material with appropriate
S.G. Krishnan et al.
substitution, doping, and defect structure tailoring as a cheaper elec­
trode. Comparatively larger attempts were devoted to exploring the
potential of MgCo2O4 as a battery-type electrode for battery-
supercapacitor hybrids. However, the eight MgCo2O4 morphologies re­
ported so far could show only up to ~26% of its theoretical capacitance;
which, according to EIS studies, are due to higher electrode resistance
and charge transfer resistance owing to its unoptimized surface and pore
structure. Nevertheless, this large achievement gap between the lithium
ion storage capability and supercapacitive ion storage capability offers
enormous opportunities to develop this material as a SCAP electrode
through appropriate material modification. Although reports show
almost 100% achievement of capacity in the initial cycles, the inert MgO
layer formation considerably lowers the material’s recyclability. Recent
researches on magnesium rechargeable batteries (MRBs) determined
desirable cathode properties for MgCo2O4. The main hindrance in
achieving the extended cycle life stability of MgCo2O4 in MRB is
determining suitable electrolyte. Typically magnesium salt electrolytes
such as Mg(ClO4) and Mg(BF4)2 could passivate the transport of Mg2+
ions forming surface films over Mg metal. The development of new
electrolytes could improve the performance of MgCo2O4 as a cathode for
MRBs.
8. Recommendations
We have the following recommendations for developing this mate­
rial for its practical deployability from the critical analysis embodied in
this article on the charge storability in the MgCo2O4 electrode.
(i) Adopting a suitable surfactant during synthesis and optimizing
the reaction temperature, the agglomeration of nanoparticles
could be reduced, thereby increasing its porosity. Apart from the
standard hydrothermal method, microwave-assisted or micro­
wave synthesis of MgCo2O4 could also increase the energy stor­
age capabilities of MgCo2O4. Few important aspects still missing
on the synthesis of MgCo2O4 are (a) thorough processing –
property correlation, (b) distribution of cation (either random or
ordered) in the material and understanding their role in deter­
mining the final morphology, and (c) a through structure-
property correlation as a function of cation distribution aimed
to understand the best charge storage conditions in MgCo2O4
electrode. This understanding would help identify the conditions
for the synthesis of the 1D morphology of MgCo2O4 such as
nanowires and nanorods, which are shown to be superior for
charge storability due to improved electrolyte-electrode ion/
electron transportation as well as anisotropic charge movement
in the electrode.
(ii) Material modification of cobalt oxide with appropriate substitu­
tion and replacement could be more economical and efficient for
the energy storage process. As cobalt is a rare material, substi­
tution for either partial or full replacement could address the cost
issue and tailor desired materials properties as a charge storing
electrode.
(iii) A theoretical investigation of the difference in conductivity due
to Mg2+ substitution in the Co3O4 spinel structure and its energy
storage sites (MgCo2O4) could improve the achieved capacitance
for energy storage applications. A DFT calculation on the band
structure and bonding details considering the inverse spinel
structure of MgCo2O4 has not been reported; such calculations on
the variation of band structure and bonding characteristics as a
function of Mg substitution are expected to establish the factors
affecting the charge storability in this material.
(iv) Aqueous electrolytes are most commonly reported in SCAP as
well as ASC studies. However, use of various electrolytes, espe­
cially involving Mg salt such as MgCl2 could increase the Mg ion
intercalation, thus increasing the capacitance. Recent research on
electrolytes proves the edge of acetate electrolytes and redox
23
Renewable and Sustainable Energy Reviews 141 (2021) 110798
electrolytes on carbon, proving that the carbon’s pseudocapaci­
tive property could be increased [53]. Therefore, acetate elec­
trolytes could also increase the redox reactions, thereby
improving the energy storage capacity. The mixing of polymer
with the redox or acetate electrolytes could also help design
flexible asymmetric supercapacitors with MgCo2O4 as a positive
electrode. The stability of MgCo2O4 electrodes for SCAP appli­
cations is an issue. However, the determination of an appropriate
proportion of rGO addition to MgCo2O4 could improve its cycling
stability.
(v) The practical applications of LIBs require the reduction of charge-
discharge voltages of MgCo2O4. The design of MgCo2O4 with a
proper pore size and employing the electrocatalytic technique
could reduce the voltage. Full cell studies are required upon
reducing the voltage. Also, activating the higher valence state, i.
e., Co4+ of MgCo2O4 as observed in MRBs shall increase its
voltage window, thus increasing its energy density. The explo­
ration of dual salt batteries provides future utilities for MgCo2O4
as a cathode material.
(vi) The recent development in designing an efficient Na–Mg battery
where anode and cathode were metallic Mg, and FeS2, respec­
tively, with Na/Mg dual salt electrolyte [221]. However, this
battery’s voltage window is lower (~2 V) and the use of proper
pore-sized MgCo2O4 as a cathode for Na+ ion shall improve its
energy density. A Li–Mg dual salt battery is also proposed with
MgCo2O4 as cathode material and an ionic liquid electrolyte for
both Li and Mg insertion with a voltage window of ~3V [101].
Future research in improving the energy density and commer­
cialization of these dual batteries shall accommodate MgCo2O4 as
its cathode material for “intercalation and push-out” processes.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors would like to acknowledge the research fundings
through Research Center Grant Scheme 2019 (STR-RCTR-GAMRG-001-
2019), Collaborative Research Fund (STR-RMF-MRU-001-2019), and
Fundamental research grant scheme of the Ministry of Higher Educa­
tion, Malaysia (FRGS/1/2019/STG07/UMP/01/1). The authors also
thank Dr. Anju V. Nair, for her valuable inputs in the manuscript.
References
[1] Gordon P. Global energy storage market to reach $500 billion by 2025 – report.
https://www.smart-energy.com. https://www.smart-energy.com/industry-sector
s/storage/global-energy-storage-market-to-reach-500-billion-by-2025-report/.
[2] Hodgson J. Battery electric vehicles on the fast track to reach an installed base of
over 100 million by 2029. https://www.abiresearch.com/. https://www.abirese
arch.com/press/battery-electric-vehicles-fast-track-reach-installed-base-over-
100-million-2029/.
[3] González A, Goikolea E, Barrena JA, Mysyk R. Review on supercapacitors:
technologies and materials. Renew Sustain Energy Rev 2016;58:1189–206.
[4] Hannan MA, Azidin FA, Mohamed A. Hybrid electric vehicles and their
challenges: a review. Renew Sustain Energy Rev 2014;29:135–50.
[5] Rong H, Chen T, Shi R, Zhang Y, Wang Z. Hierarchical NiCo2O4@NiCo2S4
nanocomposite on Ni foam as an electrode for hybrid supercapacitors. ACS
Omega 2018;3:5634–42.
[6] Huie MM, Bock DC, Takeuchi ES, Marschilok AC, Takeuchi KJ. Cathode materials
for magnesium and magnesium-ion based batteries. Coord Chem Rev 2015;287:
15–27.
[7] Chayambuka K, Mulder G, Danilov DL, Notten PHL. Sodium-ion battery materials
and electrochemical properties reviewed. Adv Energy Mater 2018;8:1800079.
[8] Yin X, Sarkar S, Shi S, Huang Q-A, Zhao H, Yan L, et al. Recent progress in
advanced organic electrode materials for sodium-ion batteries: synthesis,
mechanisms, challenges and perspectives. Adv Funct Mater 2020;30:1908445.
S.G. Krishnan et al.
[9] Lin M-C, Gong M, Lu B, Wu Y, Wang D-Y, Guan M, et al. An ultrafast rechargeable
aluminium-ion battery. Nature 2015;520:324–8.
[10] Ambroz F, Macdonald TJ, Nann T. Trends in aluminium-based intercalation
batteries. Adv Energy Mater 2017;7:1602093.
[11] Wild M, O’Neill L, Zhang T, Purkayastha R, Minton G, Marinescu M, et al. Lithium
sulfur batteries, a mechanistic review. Energy Environ Sci 2015;8:3477–94.
[12] Liu T, Hu H, Ding X, Yuan H, Jin C, Nai J, et al. 12 years roadmap of the sulfur
cathode for lithium sulfur batteries (2009–2020). Energy Storage Mater 2020;30:
346–66.
[13] Ma Z, Yuan X, Li L, Ma Z-F, Wilkinson DP, Zhang L, et al. A review of cathode
materials and structures for rechargeable lithium–air batteries. Energy Environ
Sci 2015;8:2144–98.
[14] Jung J-W, Cho S-H, Nam JS, Kim I-D. Current and future cathode materials for
non-aqueous Li-air (O2) battery technology – a focused review. Energy Storage
Mater 2020;24:512–28.
[15] Zhao X, Mao L, Cheng Q, Li J, Liao F, Yang G, et al. Two-dimensional spinel
structured Co-based materials for high performance supercapacitors: a critical
review. Chem Eng J 2020;387:124081.
[16] Devillers N, Jemei S, Péra M-C, Bienaimé D, Gustin F. Review of characterization
methods for supercapacitor modelling. J Power Sources 2014;246:596–608.
[17] Liu H, Liu X, Wang S, Liu H-K, Li L. Transition metal based battery-type electrodes
in hybrid supercapacitors: a review. Energy Storage Mater 2020;28:122–45.
[18] Yu L, Chen GZ. Redox electrode materials for supercapatteries. J Power Sources
2016;326:604–12.
[19] Zuo W, Li R, Zhou C, Li Y, Xia J, Liu J. Battery-supercapacitor hybrid devices:
recent progress and future prospects. Adv Sci 2017;4:1600539.
[20] Ma F, Lu J, Pu L, Wang W, Dai Y. Construction of hierarchical cobalt-
molybdenum selenide hollow nanospheres architectures for high performance
battery-supercapacitor hybrid devices. J Colloid Interface Sci 2020;563:435–46.
[21] Ji L, Medford AJ, Zhang X. Porous carbon nanofibers loaded with manganese
oxide particles: formation mechanism and electrochemical performance as
energy-storage materials. J Mater Chem 2009;19:5593–601.
[22] Fichtner M. Nanoconfinement effects in energy storage materials. Phys Chem
Chem Phys 2011;13:21186–95.
[23] Lyu L, Seong K-d, Ko D, Choi J, Lee C, Hwang T, et al. Recent development of
biomass-derived carbons and composites as electrode materials for
supercapacitors. Mater Chem Front 2019;3:2543–70.
[24] Tsang CHA, Huang H, Xuan J, Wang H, Leung D. Graphene materials in green
energy applications: recent development and future perspective. Renew Sustain
Energy Rev 2020;120:109656.
[25] Chen S, Qiu L, Cheng H-M. Carbon-based fibers for advanced electrochemical
energy storage devices. Chem Rev 2020;120:2811–78.
[26] Yar A, Dennis JO, Mohamed Saheed MS, Mohamed NM, Irshad MI, Mumtaz A,
et al. Physical reduction of graphene oxide for supercapacitive charge storage.
J Alloys Compd 2020;822:153636.
[27] Chime UK, Nkele AC, Ezugwu S, Nwanya AC, Shinde N, Kabede M, et al. Recent
progress in nickel oxide-based electrodes for high-performance supercapacitors.
Curr Opin Electrochem 2020;21:175–81.
[28] Shinde PA, Jun SC. Review on recent progress in the development of tungsten
oxide based electrodes for electrochemical energy storage. ChemSusChem 2020;
13:11–38.
[29] Afif A, Rahman SM, Azad AT, Zaini J, Islan MA, Azad AK. Advanced materials and
technologies for hybrid supercapacitors for energy storage–a review. J Energy
Storage 2019;25:100852.
[30] Shin J, Seo JK, Yaylian R, Huang A, Meng YS. A review on mechanistic
understanding of MnO2 in aqueous electrolyte for electrical energy storage
systems. Int Mater Rev 2019:1–32.
[31] Majumdar D, Maiyalagan T, Jiang Z. Recent progress in ruthenium oxide-based
composites for supercapacitor applications. ChemElectroChem 2019;6:4343–72.
[32] Harilal M, Vidyadharan B, Misnon II, Anilkumar GM, Lowe A, Ismail J, et al. One-
dimensional assembly of conductive and capacitive metal oxide electrodes for
high-performance asymmetric supercapacitors. ACS Appl Mater Interfaces 2017;
9:10730–42.
[33] Harilal M, Krishnan SG, Vijayan BL, Venkatashamy Reddy M, Adams S,
Barron AR, et al. Continuous nanobelts of nickel oxide–cobalt oxide hybrid with
improved capacitive charge storage properties. Mater Des 2017;122:376–84.
[34] Vijayan BL, Krishnan SG, Zain NKM, Harilal M, Yar A, Misnon II, et al. Large scale
synthesis of binary composite nanowires in the Mn2O3-SnO2 system with
improved charge storage capabilities. Chem Eng J 2017;327:962–72.
[35] Pal B, Bakr ZH, Krishnan SG, Yusoff MM, Jose R. Large scale synthesis of 3D
nanoflowers of SnO2/TiO2 composite via electrospinning with synergistic
properties. Mater Lett 2018;225:117–21.
[36] Xiong X, Ding D, Chen D, Waller G, Bu Y, Wang Z, et al. Three-dimensional
ultrathin Ni(OH)2 nanosheets grown on nickel foam for high-performance
supercapacitors. Nanomater Energy 2015;11:154–61.
[37] Gurav KV, Patil UM, Shin SW, Agawane GL, Suryawanshi MP, Pawar SM, et al.
Room temperature chemical synthesis of Cu(OH)2 thin films for supercapacitor
application. J Alloys Compd 2013;573:27–31.
[38] Xue T, Wang X, Lee J-M. Dual-template synthesis of Co(OH)2 with mesoporous
nanowire structure and its application in supercapacitor. J Power Sources 2012;
201:382–6.
[39] Kim H-C, Hwang Y-K, Seo SJ, Huh S. Gas sorption and supercapacitive properties
of hierarchical porous graphitic carbons prepared from the hard-templating of
mesoporous ZnO/Zn(OH)2 composite spheres. J Colloid Interface Sci 2020;564:
193–203.
24
Renewable and Sustainable Energy Reviews 141 (2021) 110798
[40] Aziz RA, Misnon II, Chong KF, Yusoff MM, Jose R. Layered sodium titanate
nanostructures as a new electrode for high energy density supercapacitors.
Electrochim Acta 2013;113:141–8.
[41] Theerthagiri J, Senthil RA, Nithyadharseni P, Lee SJ, Durai G, Kuppusami P, et al.
Recent progress and emerging challenges of transition metal sulfides based
composite electrodes for electrochemical supercapacitive energy storage. Ceram
Int 2020;46:14317–45.
[42] Abraham AM, Lonkar SP, Pillai VV, Alhassan SM. Three-Dimensional MoS2
nanodot-impregnated nickel foam electrodes for high-performance
supercapacitor applications. ACS Omega 2020;5:11721–9.
[43] Chaudhari S, Sharma Y, Archana PS, Jose R, Ramakrishna S, Mhaisalkar S, et al.
Electrospun polyaniline nanofibers web electrodes for supercapacitors. J Appl
Polym Sci 2013;129:1660–8.
[44] Misnon II, Jose R. Synthesis and electrochemical evaluation of the PANI/δ-MnO2
electrode for high performing asymmetric supercapacitors. New J Chem 2017;41:
6574–84.
[45] Nyholm L, Nyström G, Mihranyan A, Strømme M. Toward flexible polymer and
paper-based energy storage devices. Adv Mater 2011;23:3751–69.
[46] Wang J, Wu Z, Hu K, Chen X, Yin H. High conductivity graphene-like MoS2/
polyaniline nanocomposites and its application in supercapacitor. J Alloys Compd
2015;619:38–43.
[47] Izwan Misnon I, Krishnan SG, Jose R. Thin chemisorbed polyaniline film on cobalt
oxide as an electrode for hybrid energy storage devices. Chemistry 2020;5:
7973–83.
[48] Diggikar RS, Ambekar JD, Kulkarni MV, Kale BB. Nanocrystalline silver vanadium
sulfide (SVS) anchored polyaniline (PANI): new nanocomposite system for
supercapacitor. New J Chem 2013;37:3236–43.
[49] Wang D-G, Liang Z, Gao S, Qu C, Zou R. Metal-organic framework-based
materials for hybrid supercapacitor application. Coord Chem Rev 2020;404:
213093.
[50] Liu Y, Xu X, Shao Z. Metal-organic frameworks derived porous carbon, metal
oxides and metal sulfides-based compounds for supercapacitors application.
Energy Storage Mater 2020;26:1–22.
[51] Mohd Zain NK, Vijayan BL, Misnon II, Das S, Karuppiah C, Yang C-C, et al. Direct
growth of triple cation metal–organic framework on a metal substrate for
electrochemical energy storage. Ind Eng Chem Res 2019;58:665–74.
[52] Yang Y. A mini-review: emerging all-solid-state energy storage electrode
materials for flexible devices. Nanoscale 2020;12:3560–73.
[53] Wang G, Zhang L, Zhang J. A review of electrode materials for electrochemical
supercapacitors. Chem Soc Rev 2012;41:797–828.
[54] Liu C, Li F, Ma LP, Cheng HM. Advanced materials for energy storage. Adv Mater
2010;22:E28–62.
[55] Vidhyadharan B, Misnon II, Aziz RA, Padmasree KP, Yusoff MM, Jose R. Superior
supercapacitive performance in electrospun copper oxide nanowire electrodes.
J Mater Chem A 2014;2:6578.
[56] Jose R, Krishnan SG, Vidyadharan B, Misnon II, Harilal M, Aziz RA, et al.
Supercapacitor electrodes delivering high energy and power densities. Mater
Today: Proceedings. 2016;3:S48–56.
[57] Kate RS, Khalate SA, Deokate RJ. Overview of nanostructured metal oxides and
pure nickel oxide (NiO) electrodes for supercapacitors: a review. J Alloys Compd
2018;734:89–111.
[58] Chen J, Xu Z, Zhu H, Liu R, Song X, Song Q, et al. An ultrafast supercapacitor built
by Co3O4 with tertiary hierarchical architecture. Vacuum 2020;174:109219.
[59] Mao Y, Shen X, Wu Z, Zhu L, Liao G. Preparation of Co3O4 hollow microspheres
by recycling spent lithium-ion batteries and their application in electrochemical
supercapacitors. J Alloys Compd 2020;816:152604.
[60] Zhang R, Gao S, Zhou T, Tu J, Zhang T. Facile preparation of hierarchical
structure based on p-type Co3O4 as toluene detecting sensor. Appl Surf Sci 2020;
503:144167.
[61] Sun H, Lv H. Facet engineering of Nano-Co3O4 for catalytic and gas sensor
performance: a mechanism insight. J Alloys Compd 2020;823:153742.
[62] He D, Song X, Li W, Tang C, Liu J, Ke Z, et al. Active electron density modulation
of Co3O4-based catalysts enhances their oxygen evolution performance. Angew
Chem Int Ed 2020;59:6929–35.
[63] Liu W, Liu R, Zhang X. Controllable synthesis of 3D hierarchical Co3O4 catalysts
and their excellent catalytic performance for toluene combustion. Appl Surf Sci
2020;507:145174.
[64] Meher SK, Rao GR. Ultralayered Co3O4 for high-performance supercapacitor
applications. J Phys Chem C 2011;115:15646–54.
[65] Vidyadharan B, Aziz RA, Misnon II, Anil Kumar GM, Ismail J, Yusoff MM, et al.
High energy and power density asymmetric supercapacitors using electrospun
cobalt oxide nanowire anode. J Power Sources 2014;270:526–35.
[66] Yang J, Xu X, Zhou X, Jiang S, Chen W, Shi S, et al. Ultrasmall Co3O4
nanoparticles confined in P, N-doped carbon matrices for high-performance
supercapacitors. J Phys Chem C 2020;124:9225–32.
[67] UmaSudharshini A, Bououdina M, Venkateshwarlu M, Manoharan C,
Dhamodharan P. Low temperature solvothermal synthesis of pristine Co3O4
nanoparticles as potential supercapacitor. Surf Interfaces 2020;19:100535.
[68] Liu W, Li X, Zhu M, He X. High-performance all-solid state asymmetric
supercapacitor based on Co3O4 nanowires and carbon aerogel. J Power Sources
2015;282:179–86.
[69] Yan Q, Li X, Zhao Q, Chen G. Shape-controlled fabrication of the porous Co3O4
nanoflower clusters for efficient catalytic oxidation of gaseous toluene. J Hazard
Mater 2012;209:385–91.
S.G. Krishnan et al.
[70] Qing X, Liu S, Huang K, Lv K, Yang Y, Lu Z, et al. Facile synthesis of Co3O4
nanoflowers grown on Ni foam with superior electrochemical performance.
Electrochim Acta 2011;56:4985–91.
[71] Soomro RA, Ibupoto ZH, Sherazi STH, Abro MI, Willander M, Mahesar SA, et al.
Glycine-assisted preparation of Co3O4 nanoflakes with enhanced performance for
non-enzymatic glucose sensing. Mater Express 2015;5:437–44.
[72] Raj S, Srivastava SK, Kar P, Roy P. In situ growth of Co3O4 nanoflakes on reduced
graphene oxide-wrapped Ni-foam as high performance asymmetric
supercapacitor. Electrochim Acta 2019;302:327–37.
[73] Xiao Y, Liu S, Li F, Zhang A, Zhao J, Fang S, et al. 3D hierarchical Co3O4 twin-
spheres with an urchin-like structure: large-scale synthesis, multistep-splitting
growth, and electrochemical pseudocapacitors. Adv Funct Mater 2012;22:
4052–9.
[74] Luo X, Zhong M, He P, Shao J, Wang Q, Li K, et al. Transformation of 2D Co-LDH
into 3D hierarchical hollow Co3O4 polyhedral arrays with enhanced
electrochemical performance for supercapacitors. J Alloys Compd 2020;826:
154241.
[75] Guragain D, Zequine C, Gupta RK, Mishra SR. Facile synthesis of bio-template
tubular MCo2O4 (M= Cr, Mn, Ni) microstructure and its electrochemical
performance in aqueous electrolyte. Processes 2020;8:343.
[76] Chen H, Du X, Wu R, Wang Y, Sun J, Zhang Y, et al. Facile hydrothermal synthesis
of porous MgCo2O4 nanoflakes as an electrode material for high-performance
asymmetric supercapacitors. Nanoscale Adv 2020;2:3263–75.
[77] Zhao X, Mao L, Cheng Q, Li J, Liao F, Yang G, et al. Recent advances in two-
dimensional spinel structured Co-based materials for high performance
supercapacitors: a critical review. Chem Eng J 2020:124081.
[78] Yuan C, Li J, Hou L, Zhang X, Shen L, Lou XW. Ultrathin mesoporous NiCo2O4
nanosheets supported on Ni foam as advanced electrodes for supercapacitors. Adv
Funct Mater 2012;22:4592–7.
[79] Ma S, Sun L, Cong L, Gao X, Yao C, Guo X, et al. Multiporous MnCo2O4
microspheres as an efficient bifunctional catalyst for nonaqueous Li–O2 batteries.
J Phys Chem C 2013;117:25890–7.
[80] Sharma Y, Sharma N, Subba Rao GV, Chowdari BVR. Studies on spinel cobaltites,
FeCo2O4 and MgCo2O4 as anodes for Li-ion batteries. Solid State Ionics 2008;179:
587–97.
[81] Reddy MV, Rajesh M, Adams S, Chowdari BVR. Effect of initial reactants and
reaction temperature on molten salt synthesis of CuCo2O4 and its sustainable
energy storage properties. ACS Sustainable Chem Eng 2016;4:3076–86.
[82] Reddy M, Kenrick K, Wei TY, Chong GY, Leong GH, Chowdari B. Nano-ZnCo2O4
material preparation by molten salt method and its electrochemical properties for
lithium batteries. J Electrochem Soc 2011;158:A1423.
[83] Cabello M, Nacimiento F, González JR, Ortiz G, Alcántara R, Lavela P, et al.
Advancing towards a veritable calcium-ion battery: CaCo2O4 positive electrode
material. Electrochem Commun 2016;67:59–64.
[84] Kim KJ, Park YR. Optical investigation of charge-transfer transitions in spinel
Co3O4. Solid State Commun 2003;127:25–8.
[85] Liu S, Ni D, Li H-F, Hui KN, Ouyang C-Y, Jun SC. Effect of cation substitution on
the pseudocapacitive performance of spinel cobaltite MCo2O4 (M = Mn, Ni, Cu,
and Co). J Mater Chem A 2018;6:10674–85.
[86] Xu JM, Cheng JP. The advances of Co3O4 as gas sensing materials: a review.
J Alloys Compd 2016;686:753–68.
[87] Cui B, Lin H, Liu Y-z, Li J-b, Sun P, Zhao X-c, et al. Photophysical and
photocatalytic properties of core-ring structured NiCo2O4 nanoplatelets. J Phys
Chem C 2009;113:14083–7.
[88] Cheng X, Zhou X, Liu Z, Zhang Y, Liu Q, Liu Q, et al. Hydrothermal solvothermal
synthesis and microwave absorbing study of MCo2O4 (M= Mn, Ni) microparticles.
Adv Appl Ceram 2019;118:466–72.
[89] Chen H-Y, Chen J-H. Preparation of p-type CuCo2O4 thin films by sol-gel
processing. Mater Lett 2017;188:63–5.
[90] Guo H, Chen J, Weng W, Wang Q, Li S. Facile template-free one-pot fabrication of
ZnCo2O4 microspheres with enhanced photocatalytic activities under visible-light
illumination. Chem Eng J 2014;239:192–9.
[91] Silambarasan M, Ramesh PS, Geetha D, Venkatachalam V. A report on 1D
MgCo2O4 with enhanced structural, morphological and electrochemical
properties. J Mater Sci Mater 2017;28:6880–8.
[92] Ekebas E, Cetin A, Önal AM, Esenturk EN. Magnesium substituted cobalt spinel
nanostructures for electrocatalytic water oxidation. J Appl Electrochem 2019;49:
315–25.
[93] Jadhav HS, Roy A, Thorat GM, Seo JG. Facile and cost-effective growth of a
highly efficient MgCo2O4 electrocatalyst for methanol oxidation. Inorg Chem
Front 2018;5:1115–20.
[94] Li G, Liu X, Bai W. Fabrication of porous MgCo2O4 with rod-like morphology and
its superb catalytic activity towards ammonium perchlorate thermal
decomposition. Mater Res Express 2018;5:035036.
[95] Zamudio MA, Bensaid S, Fino D, Russo N. Influence of the MgCo2O4 preparation
method on N2O catalytic decomposition. Ind Eng Chem Res 2011;50:2622–7.
[96] Guan X, Yu Y, Li X, Chen D, Luo P, Zhang Y, et al. Hierarchically porous MgCo2O4
nanochain networks: template-free synthesis and catalytic application. Mater Res
Express 2018;5:015002.
[97] Li Y, Zhang T, Li J, Li C, Guo Z, Ma H. Three-dimensional nickel foam templated
MgCo2O4 nanowires as an efficient catalyst for the thermal decomposition of
ammonium perchlorate. J Solid State Chem 2020;288:121426.
[98] Rathinavel S, Vadivel S, Balaji G. Development of ethanol and acetone gas sensing
performance of MgCo2O4 nanosensors by clad modified fiber optical method. Opt
Fiber Technol 2019;48:218–24.
25
Renewable and Sustainable Energy Reviews 141 (2021) 110798
[99] Zhang P, Wang J, Jia Y, Li W, Tan X, Zhang D, et al. Encapsulating spinel
nancrystals in Laponite cages and applications in molecular oxidation of
cyclohexane. Appl Clay Sci 2019;181:105226.
[100] Liu J, Liang H, Zhang Y, Wu G, Wu H. Facile synthesis of ellipsoid-like MgCo2O4/
Co3O4 composites for strong wideband microwave absorption application.
Compos B Eng 2019;176:107240.
[101] Ichitsubo T, Okamoto S, Kawaguchi T, Kumagai Y, Oba F, Yagi S, et al. Toward
“rocking-chair type” Mg–Li dual-salt batteries. J Mater Chem A 2015;3:10188–94.
[102] Yoo HD, Shterenberg I, Gofer Y, Gershinsky G, Pour N, Aurbach D. Mg
rechargeable batteries: an on-going challenge. Energy Environ Sci 2013;6:
2265–79.
[103] Kamioka N, Ichitsubo T, Uda T, Imashuku S, Taninouchi Y-k, Matsubara E.
Synthesis of spinel-type magnesium cobalt oxide and its electrical conductivity.
Mater Trans 2008;49:824–8.
[104] Ichitsubo T, Adachi T, Yagi S, Doi T. Potential positive electrodes for high-voltage
magnesium-ion batteries. J Mater Chem 2011;21:11764–72.
[105] Chen D, Wang Q, Wang R, Shen G. Ternary oxide nanostructured materials for
supercapacitors: a review. J Mater Chem A 2015;3:10158–73.
[106] Zhi M, Xiang C, Li J, Li M, Wu N. Nanostructured carbon–metal oxide composite
electrodes for supercapacitors: a review. Nanoscale 2013;5:72–88.
[107] Deng Y, Xie Y, Zou K, Ji X. Review on recent advances in nitrogen-doped carbons:
preparations and applications in supercapacitors. J Mater Chem A 2016;4:
1144–73.
[108] Chen K, Xue D. Materials chemistry toward electrochemical energy storage.
J Mater Chem A 2016;4:7522–37.
[109] Zhong C, Deng Y, Hu W, Qiao J, Zhang L, Zhang J. A review of electrolyte
materials and compositions for electrochemical supercapacitors. Chem Soc Rev
2015;44:7484–539.
[110] Opitz A, Badami P, Shen L, Vignarooban K, Kannan AM. Can Li-Ion batteries be
the panacea for automotive applications? Renew Sustain Energy Rev 2017;68
(Part 1):685–92.
[111] Conway BE. Electrochemical supercapacitors: scientific fundamentals and
technological applications. second ed. New York: Kluwer Academic/Plenum
Publishers; 1997.
[112] Abioye AM, Ani FN. Recent development in the production of activated carbon
electrodes from agricultural waste biomass for supercapacitors: a review. Renew
Sustain Energy Rev 2015;52:1282–93.
[113] Pal B, Yang S, Ramesh S, Thangadurai V, Jose R. Electrolyte selection for
supercapacitive devices: a critical review. Nanoscale Adv 2019;1:3807–35.
[114] Chang J-K, Tsai W-T. Material characterization and electrochemical performance
of hydrous manganese oxide electrodes for use in electrochemical
pseudocapacitors. J Electrochem Soc 2003;150:A1333.
[115] Gao Y, Chen S, Cao D, Wang G, Yin J. Electrochemical capacitance of Co3O4
nanowire arrays supported on nickel foam. J Power Sources 2010;195:1757–60.
[116] Zhang J, Zhang G, Luo W, Sun Y, Jin C, Zheng W. Graphitic carbon coated CuO
hollow nanospheres with penetrated mesochannels for high-performance
asymmetric supercapacitors. ACS Sustainable Chem Eng 2017;5:105–11.
[117] Brousse T, Bélanger D, Long JW. To be or not to be pseudocapacitive?
J Electrochem Soc 2015;162:A5185–9.
[118] Cherusseri J, Pandey D, Thomas J. Symmetric, asymmetric, and battery-type
supercapacitors using two-dimensional nanomaterials and composites. Batteries
& Supercaps 2020;3:860.
[119] Goodenough JB, Park K-S. The li-ion rechargeable battery: a perspective. J Am
Chem Soc 2013;135:1167–76.
[120] Krishnan SG, Reddy MV, Harilal M, Vidyadharan B, Misnon II, Rahim MHA, et al.
Characterization of MgCo2O4 as an electrode for high performance
supercapacitors. Electrochim Acta 2015;161:312–21.
[121] Krishnan SG, Harilal M, Misnon II, Reddy MV, Adams S, Jose R. Effect of
processing parameters on the charge storage properties of MgCo2O4 electrodes.
Ceram Int 2017;43:12270–9.
[122] Ndione PF, Shi Y, Stevanovic V, Lany S, Zakutayev A, Parilla PA, et al. Control of
the electrical properties in spinel oxides by manipulating the cation disorder. Adv
Funct Mater 2014;24:610–8.
[123] Zhao Q, Yan Z, Chen C, Chen J. Spinels: controlled preparation, oxygen
reduction/evolution reaction application, and beyond. Chem Rev 2017;117:
10121–211.
[124] Shi X, Bernasek SL, Selloni A. Formation, electronic structure, and defects of Ni
substituted spinel cobalt oxide: a DFT+U study. J Phys Chem C 2016;120:
14892–8.
[125] Wang Y, Sun J, Li S, Zhang Y, Xu C, Chen H. Hydrothermal synthesis of flower-
like MgCo2O4 porous microstructures as high-performance electrode material for
asymmetric supercapacitors. J Alloys Compd 2020;824:153939.
[126] Dong L, Xu C, Li Y, Huang Z-H, Kang F, Yang Q-H, et al. Flexible electrodes and
supercapacitors for wearable energy storage: a review by category. J Mater Chem
A 2016;4:4659–85.
[127] Okamoto S, Ichitsubo T, Kawaguchi T, Kumagai Y, Oba F, Yagi S, et al.
Intercalation and push-out process with spinel-to-rocksalt transition on Mg
insertion into spinel oxides in magnesium batteries. Adv Sci 2015;2:1500072.
[128] Cui L, Huang L, Ji M, Wang Y, Shi H, Zuo Y, et al. High-performance MgCo2O4
nanocone arrays grown on three-dimensional nickel foams: preparation and
application as binder-free electrode for pseudo-supercapacitor. J Power Sources
2016;333:118–24.
[129] Krishnan SG, Harilal M, Pal B, Misnon II, Karuppiah C, Yang C-C, et al. Improving
the symmetry of asymmetric supercapacitors using battery-type positive
electrodes and activated carbon negative electrodes by mass and charge balance.
J Electroanal Chem 2017;805:126–32.
S.G. Krishnan et al.
[130] Zhou M, Cai L, Bajdich M, García-Melchor M, Li H, He J, et al. Enhancing catalytic
CO oxidation over Co3O4 nanowires by substituting Co2+ with Cu2+. ACS Catal
2015;5:4485–91.
[131] Wu G, Wang J, Ding W, Nie Y, Li L, Qi X, et al. A strategy to promote the
electrocatalytic activity of spinels for oxygen reduction by structure reversal.
Angew Chem Int Ed 2016;55:1340–4.
[132] Wei C, Feng Z, Baisariyev M, Yu L, Zeng L, Wu T, et al. Valence change ability and
geometrical occupation of substitution cations determine the pseudocapacitance
of spinel ferrite XFe2O4 (X = Mn, Co, Ni, Fe). Chem Mater 2016;28:4129–33.
[133] Reddy MV, Mauger A, Julien CM, Paolella A, Zaghib K. Brief history of early
lithium-battery development. Materials 2020;13:1884.
[134] Peters JF, Baumann M, Zimmermann B, Braun J, Weil M. The environmental
impact of Li-Ion batteries and the role of key parameters – a review. Renew
Sustain Energy Rev 2017;67:491–506.
[135] Armand M, Touzain P. Graphite intercalation compounds as cathode materials.
Mater Sci Eng 1977;31:319–29.
[136] Yang Y, Yuan W, Zhang X, Ke Y, Qiu Z, Luo J, et al. A review on structuralized
current collectors for high-performance lithium-ion battery anodes. Appl Energy
2020;276:115464.
[137] Kucinskis G, Bajars G, Kleperis J. Graphene in lithium ion battery cathode
materials: a review. J Power Sources 2013;240:66–79.
[138] Zuo X, Zhu J, Müller-Buschbaum P, Cheng Y-J. Silicon based lithium-ion battery
anodes: a chronicle perspective review. Nanomater Energy 2017;31:113–43.
[139] Meshram P, Mishra A, Abhilash Sahu R. Environmental impact of spent lithium
ion batteries and green recycling perspectives by organic acids – a review.
Chemosphere 2020;242:125291.
[140] Tian H, Qin P, Li K, Zhao Z. A review of the state of health for lithium-ion
batteries: research status and suggestions. J Clean Prod 2020;261:120813.
[141] Xu G, Shangguan X, Dong S, Zhou X, Cui G. Formulation of blended-lithium-salt
electrolytes for lithium batteries. Angew Chem Int Ed 2020;59:3400–15.
[142] Besenhard JO, Fritz HP. The electrochemistry of black carbons. Angew Chem Int
Ed 1983;22:950–75.
[143] Ebert LB. Intercalation compounds of graphite. Annu Rev Mater Sci 1976;6:
181–211.
[144] Schlögl R. Graphite—a unique host lattice. In: Müller-Warmuth W, Schöllhorn R,
editors. Progress in intercalation research. The Netherlands: Springer; 1994.
p. 83.
[145] Winter M, Besenhard JO, Spahr ME, Novák P. Insertion electrode materials for
rechargeable lithium batteries. Adv Mater 1998;10:725–63.
[146] Dahn JR. Phase diagram of LiXC6. Phys Rev B 1991;44:9170–7.
[147] Dahn JR, Zheng T, Liu Y, Xue JS. Mechanisms for lithium insertion in
carbonaceous materials. Science 1995;270:590–3.
[148] Aurbach D, Markovsky B, Weissman I, Levi E, Ein-Eli Y. On the correlation
between surface chemistry and performance of graphite negative electrodes for Li
ion batteries. Electrochim Acta 1999;45:67–86.
[149] Daumas N, Herold A. Relations between phase concept and reaction mechanics in
graphite insertion compounds. Acad Sci Ser C 1969;268:373.
[150] Sethuraman VA, Hardwick LJ, Srinivasan V, Kostecki R. Surface structural
disordering in graphite upon lithium intercalation/deintercalation. J Power
Sources 2010;195:3655–60.
[151] Lu L, Han X, Li J, Hua J, Ouyang M. A review on the key issues for lithium-ion
battery management in electric vehicles. J Power Sources 2013;226:272–88.
[152] Feng X, Ouyang M, Liu X, Lu L, Xia Y, He X. Thermal runaway mechanism of
lithium ion battery for electric vehicles: a review. Energy Storage Mater 2018;10:
246–67.
[153] Li X, Huang J, Faghri A. A critical review of macroscopic modeling studies on LiO2
and Li–air batteries using organic electrolyte: challenges and opportunities.
J Power Sources 2016;332:420–46.
[154] Barré A, Deguilhem B, Grolleau S, Gérard M, Suard F, Riu D. A review on lithium-
ion battery ageing mechanisms and estimations for automotive applications.
J Power Sources 2013;241:680–9.
[155] Lv W, Wang Z, Cao H, Sun Y, Zhang Y, Sun Z. A critical review and analysis on the
recycling of spent lithium-ion batteries. ACS Sustainable Chem Eng 2018;6:
1504–21.
[156] Han X, Gui X, Yi T-F, Li Y, Yue C. Recent progress of NiCo2O4-based anodes for
high-performance lithium-ion batteries. Curr Opin Solid State Mater Sci 2018;22:
109–26.
[157] Wu F, Bai J, Feng J, Xiong S. Porous mixed metal oxides: design, formation
mechanism, and application in lithium-ion batteries. Nanoscale 2015;7:
17211–30.
[158] Li J, Xiong S, Liu Y, Ju Z, Qian Y. High electrochemical performance of
monodisperse NiCo2O4 mesoporous microspheres as an anode material for li-ion
batteries. ACS Appl Mater Interfaces 2013;5:981–8.
[159] Sharma Y, Sharma N, Subba Rao GV, Chowdari BVR. Nanophase ZnCo2O4 as a
high performance anode material for Li-ion batteries. Adv Funct Mater 2007;17:
2855–61.
[160] Wang W, Yang Y, Yang S, Guo Z, Feng C, Tang X. Synthesis and electrochemical
performance of ZnCo2O4 for lithium-ion battery application. Electrochim Acta
2015;155:297–304.
[161] Mondal AK, Su D, Chen S, Ung A, Kim H-S, Wang G. Mesoporous MnCo2O4 with a
flake-like structure as advanced electrode materials for lithium-ion batteries and
supercapacitors. Chem Eur J 2015;21:1526–32.
[162] Kulkarni P, Ghosh D, Balakrishna G, Rawat R, Reddy M, Adams S. Facile high
yield synthesis of MgCo2O4 and investigation of its role as anode material for
lithium ion batteries. Ceram Int 2019;45:14775–82.
26
Renewable and Sustainable Energy Reviews 141 (2021) 110798
[163] Sharma Y, Sharma N, Subba Rao GV, Chowdari BVR. Studies on spinel cobaltites,
FeCo2O4 and MgCo2O4 as anodes for Li-ion batteries. Solid State Ionics 2008;
179:587–97.
[164] Wang X, Zhai G, Wang H. Facile synthesis of MgCo2O4 nanowires as binder-free
flexible anode materials for high-performance Li-ion batteries. J Nanopart Res
2015;17:339.
[165] Reddy M, Xu Y, Rajarajan V, Ouyang T, Chowdari B. Template free facile molten
synthesis and energy storage studies on MCo2O4 (M= Mg, Mn) as anode for Li-ion
batteries. ACS Sustainable Chem Eng 2015;3:3035–42.
[166] Reddy MV, Yu C, Jiahuan F, Loh KP, Chowdari BVR. Molten salt synthesis and
energy storage studies on CuCo2O4 and CuO⋅Co3O4. RSC Adv 2012;2:9619–25.
[167] Sa N, Mukherjee A, Han B, Ren Y, Klie RF, Key B, et al. Direct observation of MgO
formation at cathode electrolyte interface of a spinel MgCo2O4 cathode upon
electrochemical Mg removal and insertion. J Power Sources 2019;424:68–75.
[168] Rahman MA, Wong YC, Song G, Wen C. A review on porous negative electrodes
for high performance lithium-ion batteries. J Porous Mater 2015;22:1313–43.
[169] Darbar D, Reddy M, Sundarrajan S, Pattabiraman R, Ramakrishna S, Chowdari B.
Anodic electrochemical performances of MgCo2O4 synthesized by oxalate
decomposition method and electrospinning technique for Li-ion battery
application. Mater Res Bull 2016;73:369–76.
[170] Shin H, Lee W-J. Multi-shelled MgCo2O4 hollow microspheres as anodes for
lithium ion batteries. J Mater Chem A 2016;4:12263–72.
[171] Wu X, Bai Y, Zeng M, Li J. Novel secondary assembled porous MgCo2O4 for high-
performance lithium storage. Mater Lett 2019;240:225–8.
[172] Wang F, Liu Y, Zhao Y, Wang Y, Wang Z, Zhang W, et al. Facile synthesis of two-
dimensional porous MgCo2O4 nanosheets as anode for lithium-ion batteries. Appl
Sci 2018;8:22.
[173] Kulkarni P, Varnika C, Tong BLY, Ghosh D, Balakrishna G, Rawat RS, et al.
Investigating the role of precipitating agents on the electrochemical performance
of MgCo2O4. J Electroanal Chem 2019;851:113403.
[174] Mei J, Liao T, Kou L, Sun Z. Two-dimensional metal oxide nanomaterials for next-
generation rechargeable batteries. Adv Mater 2017;29:1700176.
[175] Peng L, Zhang H, Fang L, Bai Y, Wang Y. Designed functional systems for high-
performance lithium-ion batteries anode: from solid to hollow, and to core–shell
nico2o4 nanoparticles encapsulated in ultrathin carbon nanosheets. ACS Appl
Mater Interfaces 2016;8:4745–53.
[176] Li Y, Wang R, Guo Z, Xiao Z, Wang H, Luo X, et al. Emerging two-dimensional
noncarbon nanomaterials for flexible lithium-ion batteries: opportunities and
challenges. J Mater Chem A 2019;7:25227–46.
[177] Yu L, Guan B, Xiao W, Lou XW. Formation of yolk-shelled Ni–Co mixed oxide
nanoprisms with enhanced electrochemical performance for hybrid
supercapacitors and lithium ion batteries. Adv Energy Mater 2015;5:1500981.
[178] Leng J, Wang Z, Li X, Guo H, Li H, Shih K, et al. Accurate construction of a
hierarchical nickel–cobalt oxide multishell yolk–shell structure with large and
ultrafast lithium storage capability. J Mater Chem A 2017;5:14996–5001.
[179] Ramaseshan R, Sundarrajan S, Jose R, Ramakrishna S. Nanostructured ceramics
by electrospinning. J Appl Phys 2007;102:111101.
[180] Gu S, Hsieh C-T, Huq MM, Hsu J-P, Li J. Synthesis of MgCo2O4-coated Li4Ti5O12
composite anodes using co-precipitation method for lithium-ion batteries. J Solid
State Electrochem 2019;23:3197–207.
[181] Wang H, Guo P, Zhou T, Wu X, Zeng M. Investigation of TiO2 surface-coating
modification of MgCo2O4 nanorods anode material. Mater Lett 2021;282:128681.
[182] Tong X, Zeng M, Li J, Liu Z. Porous Co3O4@TiO2 core-shell nanofibers as
advanced anodes for lithium ion batteries. J Alloys Compd 2017;723:129–38.
[183] Yoo HD, Shterenberg I, Gofer Y, Gershinsky G, Pour N, Aurbach D. Mg
rechargeable batteries: an on-going challenge. Energy Environ Sci 2013;6:
2265–79.
[184] Wu Y, Reddy MV, Chowdari BVR, Ramakrishna S. Electrochemical studies on
electrospun Li(Li1/3Ti5/3)O4 grains as an anode for Li-ion batteries. Electrochim
Acta 2012;67:33–40.
[185] Petnikota S, Rotte NK, Srikanth VV, Kota BS, Reddy M, Loh KP, et al.
Electrochemical studies of few-layered graphene as an anode material for Li ion
batteries. J Solid State Electrochem 2014;18:941–9.
[186] Gao P, Chen Z, Gong Y, Zhang R, Liu H, Tang P, et al. The role of cation vacancies
in electrode materials for enhanced electrochemical energy storage: synthesis,
advanced characterization, and fundamentals. Adv Energy Mater 2020;10:
1903780.
[187] Muzaffar A, Ahamed MB, Deshmukh K, Thirumalai J. A review on recent
advances in hybrid supercapacitors: design, fabrication and applications. Renew
Sustain Energy Rev 2019;101:123–45.
[188] Krishnan SG, Harilal M, Yar A, Vijayan BL, Dennis JO, Yusoff MM, et al. Critical
influence of reduced graphene oxide mediated binding of M (M = Mg, Mn) with
Co ions, chemical stability and charge storability enhancements of spinal-type
hierarchical MCo2O4 nanostructures. Electrochim Acta 2017;243:119–28.
[189] Mohd Abdah MAA, Azman NHN, Kulandaivalu S, Sulaiman Y. Review of the use
of transition-metal-oxide and conducting polymer-based fibres for high-
performance supercapacitors. Mater Des 2020;186:108199.
[190] Yan J, Li S, Lan B, Wu Y, Lee PS. Rational design of nanostructured electrode
materials toward multifunctional supercapacitors. Adv Funct Mater 2020;30:
1902564.
[191] Chen D, Jiang K, Huang T, Shen G. Recent advances in fiber supercapacitors:
materials, device configurations, and applications. Adv Mater 2020;32:1901806.
[192] Yan B, Zhang W, Qin X, Choi Y, Diao G, Jin X, et al. Salt powder assisted synthesis
of nanostructured materials and their electrochemical applications in energy
storage devices. Chem Eng J 2020;400:125895.
S.G. Krishnan et al.
[193] Wang Y, Li S, Sun J, Zhang Y, Chen H, Xu C. Simple solvothermal synthesis of
magnesium cobaltite microflowers as a battery grade material with high
electrochemical performances. Ceram Int 2019;45:14642–51.
[194] Xu J, Wang L, Sun Y, Zhang J, Zhang C, Zhang M. Fabrication of porous MgCo2O4
nanoneedle arrays/Ni foam as an advanced electrode material for asymmetric
supercapacitors. J Alloys Compd 2019;779:100–7.
[195] Vijayakumar S, Nagamuthu S, Ryu K-S. In situ preparation of MgCo2O4
nanosheets on Ni-foam as a binder-free electrode for high performance hybrid
supercapacitors. Dalton Trans 2018;47:6722–8.
[196] Anil Kumar Y, Singh S, Rana PJS, Kumar KD, Kim H-J. Facile preparation of
hierarchical MgCo2O4/MgCo2O4 nanochain array composites on Ni foam as
advanced electrode materials for supercapacitors. New J Chem 2020;44:4266–75.
[197] Xu J, Wang L, Zhang J, Qian J, Liu J, Zhang Z, et al. Fabrication of porous double-
urchin-like MgCo2O4 hierarchical architectures for high-rate supercapacitors.
J Alloys Compd 2016;688(Part B):933–8.
[198] Guan X, Wang Q, Luo P, Yu Y, Li X, Zhang Y, et al. Morphology-tuned synthesis of
MgCo2O4 arrays on graphene coated nickel foam for high-rate supercapacitor
electrode. Int J Electrochem Sci 2018;13:2272–85.
[199] Gao H, Li Y, Zhao H, Xiang J, Cao Y. A general fabrication approach on spinel
MCo2O4 (M = Co, Mn, Fe, Mg and Zn) submicron prisms as advanced positive
materials for supercapacitor. Electrochim Acta 2018;262:241–51.
[200] Gao G, Wu HB, Ding S, Liu LM, Lou XW. Hierarchical NiCo2O4 nanosheets grown
on Ni nanofoam as high-performance electrodes for supercapacitors. Small 2015;
11:804–8.
[201] Hui KN, Hui KS, Tang Z, Jadhav VV, Xia QX. Hierarchical chestnut-like MnCo2O4
nanoneedles grown on nickel foam as binder-free electrode for high energy
density asymmetric supercapacitors. J Power Sources 2016;330:195–203.
[202] Kim M, Yoo J, Kim J. Fast and reversible redox reaction of MgCo2O4 nanoneedles
on porous β-polytype silicon carbide as high performance electrodes for
electrochemical supercapacitors. J Alloys Compd 2017;710:528–38.
[203] Guan X, Luo P, Li X, Yu Y, Wang Y, Zhuo L, et al. Magnesium cobaltate
nanowires@ magnanese dioxide nanoflakes core-shell arrays on graphene-
decorated nickel foam for high-performance supercapacitors. Int J Electrochem
Sci 2018:5016–30.
[204] Krishnan SG, Rahim MHA, Jose R. Synthesis and characterization of MnCo2O4
cuboidal microcrystals as a high performance psuedocapacitor electrode. J Alloys
Compd 2016;656:707–13.
[205] Xu C, Yang H, Li Y, Wang J, Lu X. Surface engineering for advanced aqueous
supercapacitors: a review. ChemElectroChem 2020;7:586–93.
[206] Sharma P, Kumar V. Current technology of supercapacitors: a review. J Electron
Mater 2020;49:3520–32.
[207] Hillier N, Yong S, Beeby S. The good, the bad and the porous: a review of
carbonaceous materials for flexible supercapacitor applications. Energy Rep
2020;6:148–56.
[208] Peng X, Peng L, Wu C, Xie Y. Two dimensional nanomaterials for flexible
supercapacitors. Chem Soc Rev 2014;43:3303–23.
[209] Wang Y, Ma X, Li S, Sun J, Zhang Y, Chen H, et al. Facile solvothermal synthesis of
novel MgCo2O4 twinned-hemispheres for high performance asymmetric
supercapacitors. J Alloys Compd 2019:152905.
[210] Kim M, Kim J. Redox active KI solid-state electrolyte for battery-like
electrochemical capacitive energy storage based on MgCo2O4 nanoneedles on
porous β-polytype silicon carbide. Electrochim Acta 2018;260:921–31.
[211] Zhu Z, Zhang R, Lin J, Zhang K, Li N, Zhao C, et al. Ni, Zn-codoped MgCo2O4
electrodes for aqueous asymmetric supercapacitor and rechargeable Zn battery.
J Power Sources 2019;437:226941.
[213] Gao H, Lian K. Proton-conducting polymer electrolytes and their applications in
solid supercapacitors: a review. RSC Adv 2014;4:33091–113.
[214] Zhao C, Zheng W. A review for aqueous electrochemical supercapacitors. Front
Energy Res 2015;3.
[215] Yang Z, Tian J, Yin Z, Cui C, Qian W, Wei F. Carbon nanotube- and graphene-
based nanomaterials and applications in high-voltage supercapacitor: a review.
Carbon 2019;141:467–80.
[216] Béguin F, Presser V, Balducci A, Frackowiak E. Carbons and electrolytes for
advanced supercapacitors. Adv Mater 2014;26:2219–51.
27
Renewable and Sustainable Energy Reviews 141 (2021) 110798
[217] Largeot C, Portet C, Chmiola J, Taberna P-L, Gogotsi Y, Simon P. Relation
between the ion size and pore size for an electric double-layer capacitor. J Am
Chem Soc 2008;130:2730–1.
[218] Misnon II, Aziz RA, Zain NKM, Vidhyadharan B, Krishnan SG, Jose R. High
performance MnO2 nanoflower electrode and the relationship between solvated
ion size and specific capacitance in highly conductive electrolytes. Mater Res Bull
2014;57:221–30.
[219] Inamdar AI, Kim Y, Pawar SM, Kim JH, Im H, Kim H. Chemically grown, porous,
nickel oxide thin-film for electrochemical supercapacitors. J Power Sources 2011;
196:2393–7.
[220] Wang Q, Ping P, Zhao X, Chu G, Sun J, Chen C. Thermal runaway caused fire and
explosion of lithium ion battery. J Power Sources 2012;208:210–24.
[221] Walter M, Kravchyk KV, Ibáñez M, Kovalenko MV. Efficient and inexpensive
sodium–magnesium hybrid battery. Chem Mater 2015;27:7452–8.
[222] Muldoon J, Bucur CB, Gregory T. Quest for nonaqueous multivalent secondary
batteries: magnesium and beyond. Chem Rev 2014;114:11683–720.
[223] Balogun M-S, Luo Y, Qiu W, Liu P, Tong Y. A review of carbon materials and their
composites with alloy metals for sodium ion battery anodes. Carbon 2016;98:
162–78.
[224] Gregory TD, Hoffman RJ, Winterton RC. Nonaqueous electrochemistry of
magnesium applications to energy storage. J Electrochem Soc 1990;137:775–80.
[225] Aurbach D, Lu Z, Schechter A, Gofer Y, Gizbar H, Turgeman R, et al. Prototype
systems for rechargeable magnesium batteries. Nature 2000;407:724.
[226] Canepa P, Sai Gautam G, Hannah DC, Malik R, Liu M, Gallagher KG, et al.
Odyssey of multivalent cathode materials: open questions and future challenges.
Chem Rev 2017;117:4287–341.
[227] Rong Z, Malik R, Canepa P, Sai Gautam G, Liu M, Jain A, et al. Materials design
rules for multivalent ion mobility in intercalation structures. Chem Mater 2015;
27:6016–21.
[228] Ishibashi C, Mizutani Y, Ishida N, Kitamura N, Idemoto Y. Crystal and electronic
structures of MgCo2− xMnxO4 as cathode material for magnesium secondary
batteries using first-principles calculations and quantum beam measurements.
Bull Chem Soc Jpn 2019;92:1950–9.
[229] Okamoto NL, Shimokawa K, Tanimura H, Ichitsubo T. Feasible transformation of
MgCo2O4 from spinel to defect rocksalt structure under electron irradiation.
Scripta Mater 2019;167:26–30.
[230] Orikasa Y, Masese T, Koyama Y, Mori T, Hattori M, Yamamoto K, et al. High
energy density rechargeable magnesium battery using earth-abundant and non-
toxic elements. Sci Rep 2014;4:5622.
[231] Mandai T, Akita Y, Yagi S, Egashira M, Munakata H, Kanamura K. A key concept
of utilization of both non-Grignard magnesium chloride and imide salts for
rechargeable Mg battery electrolytes. J Mater Chem A 2017;5:3152–6.
[232] Ha S-Y, Lee Y-W, Woo SW, Koo B, Kim J-S, Cho J, et al. Magnesium(II) bis
(trifluoromethane sulfonyl) imide-based electrolytes with wide electrochemical
windows for rechargeable magnesium batteries. ACS Appl Mater Interfaces 2014;
6:4063–73.
[233] Fukutsuka T, Asaka K, Inoo A, Yasui R, Miyazaki K, Abe T, et al. New magnesium-
ion conductive electrolyte solution based on triglyme for reversible magnesium
metal deposition and dissolution at ambient temperature. Chem Lett 2014;43:
1788–90.
[234] Kuwata H, Matsui M, Imanishi N. Passivation layer formation of magnesium
metal negative electrodes for rechargeable magnesium batteries. J Electrochem
Soc 2017;164:A3229–36.
[235] Oishi M, Ichitsubo T, Okamoto S, Toyoda S, Matsubara E, Nohira T, et al.
Electrochemical behavior of magnesium alloys in alkali metal-tfsa ionic liquid for
magnesium-battery negative electrode. J Electrochem Soc 2014;161:A943–7.
[236] Yoo HD, Han S-D, Bolotin IL, Nolis GM, Bayliss RD, Burrell AK, et al. Degradation
mechanisms of magnesium metal anodes in electrolytes based on (CF3SO2)2N– at
high current densities. Langmuir 2017;33:9398–406.
[237] Shimokawa K, Matsumoto H, Ichitsubo T. Solvation-structure modification by
concentrating Mg(TFSA)2–MgCl2–Triglyme ternary electrolyte. J Phys Chem Lett
2018;9:4732–7.