1 s2.0 S1364032121000939 Main

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 storability (energy density) of these devices [5]. Apart from LIBs, re
searches on materials for other types of secondary batteries such as
Electrical energy storage is accomplished by storing electrical magnesium rechargeable batteries (MRBs) [6], sodium batteries [7,8],
charges and the mechanism through which they assemble in an elec aluminum batteries [9,10], lithium sulphur [11,12] and lithium-air
trode and give rise to a voltage distinguish various energy storage pro batteries [13,14], electrochemical double-layer capacitors (EDLCs)
tocols such as batteries, supercapacitors, and pseudocapacitors. One of and pseudocapacitors [15,16] (together known as supercapacitors
the incessant researches on energy storage devices is developing elec (SCs)) and battery-supercapacitor hybrids (BSHs) [17,18] (also known
trode materials characterized by a set of qualities for a particular storage as supercapattery (SCAP) or asymmetric supercapacitors (ASCs)) are in
mode. Therefore, energy storage technology would remain significant progress. In the latter BSHs, a battery-type electrode (or PCs) occupies
for several upcoming decades. The predicted market of energy storage the positive electrode and EDLC occupies the negative electrode and has
materials and devices is worth ~$500 billion by 2025 [1] and that been in tremendous attention recently due to their characteristics of
estimated for electric vehicles is ~$100 million by 2029 [2]. Among the simultaneously high energy density and power density [19,20].
cost, the electrode materials account for ~40% cost of energy storage The energy storage materials should offer a range of electrochemical
devices [3]. Consumption by this large market often end-up in limitation and surface properties for efficient energy storage [21,22]. Various
of the primary materials supply and to enhance the efficiency of the materials such as carbons (activated carbon, carbon nanotubes, and
energy storage market, cost-effective materials for energy storage ap graphene) [23–26], various metal oxides (CuO, MnO2, RuO2, NiO,
plications are constantly researched [4]. At present, the research intends Co3O4, and ZnO) [27–31] and their composites (CuO–Co3O4,
* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: [email protected] (S.G. Krishnan), [email protected] (M. Khalid), [email protected] (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
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
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
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
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
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 The theoretical capacity offered by the MgCo2O4 electrode is ~780
valency state and the semiconductor nature of these materials shall mA h g− 1, more than two times higher than the graphite. The energy
improve the electrochemical reaction. storage mechanism for MgCo2O4 as the LIB electrode involves interca
lation and conversion reaction and reversible chemical bonding [162,
MCo2 O4 + 8 Li+ + 8 e− →M + 2Co + 4Li2 O
163]. The lithium-ion intercalation occurs deeper into the electrode
M + Li2 O ↔ MO + 2Li+ + 2e− pores employing electrochemical reaction, as shown in equation (3)
2Co + 2Li2 O ↔ 2CoO + 4Li+ + 4e− (3a) [164]. Instead of eight Li+ ions as discussed for other TMCs, six Li+ ions
intercalate into the MgCo2O4 electrode according to equation (3),
2 4 4
2CoO + LiO ↔ Co3 O4 + Li+ + e− thereby having a lower theoretical capacitance than other TMCs.
3 3 3
Equation (2) provides the advantage and the disadvantage of using MgCo2 O4 + 6Li+ + 6e→2Co + MgO + 2Li2 O
MCo2O4 as a LIB anode. Although the material provides intercalation 2Co + 2Li2 O ↔ CoO + 4Li+ + 4e− (3)
sites to eight Li ions, the formation of metal oxides, along with CoO in 2 2 4 4
the subsequent steps, can reduce the conductivity of MCo2O4 after the 2CoO + Li2 O ↔ Co3 O4 + Li+ + e−
3 3 3 3
initial charge-discharge process [156]. Furthermore, these irreversible
formations of metal oxide could initiate the volume expansion and the Metal oxides formed in MgCo2O4 are also similar to other MCo2O4
peeling of anode material after larger charge-discharge cycling [157]. LIB anodes; therefore, MgCo2O4 is prone to degrading the capacity be
Therefore, a significant result of commercializing these MCo2O4 mate sides the cycling stability. The amount of MgO evolved in the reaction
rials as an anode material for LIBs is not yet initiated. determines the reaction’s capacity; the lower the MgO layer formed, the
7
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 protocols for developing an electrode of suitable porosity (mesoporous)
chemically active sites [165]. Also, solid electrolyte interphase (SEI) is and surface area are essential [168] to successfully deploy MgCo2O4 as
developed on the anode surface of the LIBs due to side reaction between anodes for LIBs. The progress in MgCo2O4 research as an electrode
lithium electrolyte solvent and salt [164] as given in the below equation material for LIBs has been summarized in Table 4.
(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
Li+ + e− + electrolyte →SEI (4)
MgCo2O4 prepared by an oxalate decomposition technique, however,
This SEI, along with the above-mentioned redox reaction involved performed inferior (736 mA h g− 1 @ 60 mA g− 1) than a benchmark
with MgCo2O4 are responsible for its cycle life, charge-discharge char material FeCo2O4 (827 mA h g− 1) processed under urea combustion
acteristics, rate capability, and safety. The researches on MgCO2O4 as an method. The irreversible capacity loss (the difference between charging
anode material for LIBs was initiated due to two reasons; (i) reducing the and discharging capacitance) after first charge-discharge cycling was
amount of Co in Co3O4 due to environmental and cost issues (ii) the 28.4% and 31%, for FeCo2O4 and MgCo2O4, respectively. The proposed
utility of NiCo2O4, ZnCo2O4, and CuCo2O4 shown improved lithiation reaction mechanism of lithium intercalation to MgCo2O4 sites included
and retention in long term cycling [82,166]. Therefore, it was assumed both the pure and lithium intercalated phases (LiXMgCo2O4). Larger
that replacing one of the Co atoms with Mg2+ provides an improved intercalation of Li to MgCo2O4 lattice shall disintegrate its crystal lattice
anode material than Co3O4 even though Mg is electrochemically resulting in the formation of MgO nanoparticles along with Co and Li2O
redundant to Li intercalation. As expected, the initial report of MgCo2O4 formation [80]. Therefore, MgCo2O4 showed higher capacity fading due
as a negative electrode (anode) for LIBs was not very much promising to the inert MgO layer formation near the electrode surface; the elec
[80]. As mentioned earlier, its inferior performance has been identified trode retained only 0.9 mol of cyclable lithium after 28 cycles of
as the inertness of Mg2+ to Li intercalation as Mg2+ ions cannot be charge-discharge process. Research for the modification of morphology,
transformed to MgO due to the higher bond energy of MgO. However, surface area, the porosity of MgCo2O4 as LIB anode, and the techniques
recent studies determined that the formation of a lower quantity of MgO for reducing the formation MgO layer inside it remained idle until 2015.
layers near the electrode surface shall be reduced by modifying the Researches proved that the transformation to nano-from macro- and
anode-electrolyte interface [167]. Therefore, suitable material synthesis micron-sized materials improved the Li+ intercalation to the vacant
8
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
material sites, which increases the capacity [174]. In addition to this, the improved precipitating agent than KOH for improved porosity and Li-
interconnected structures of nanomaterials such as nanowires, nano ion charge storage [173]. Microspheres with multi shelled porous
tubes, and nanosheets could offer improved Li+ transportation, and limit structure combined both meso and macropores with an appreciable
the volumetric changes during cycling processes [175,176]. Moreover, surface area (~41 m2 g− 1) provided improved Li+ transportation
tailoring these nanostructures’ porosity enhances the surface area and channels and intercalation sites [170]. The maximum specific capacity
the pore size of the material, which further improves the active achieved is 1216 mA h g− 1 at 0.2 A g− 1 higher than its theoretical
electrode-electrolyte interface increasing the lithium charge storage capacitance proving a higher amount of Li+ intercalation. The inter
process [177,178]. Therefore, researches after 2015, focused on devel esting part of the research is the higher cycling stability (~115% after
oping nanomaterials with varied morphologies (Table 4) and porosities. 100 cycles), showing negligible MgO evolution during cycling. Similar
Improvement in capacity to 940 mA h g− 1 at a higher density 2.5 A g− 1 cycling stability (~109% after 60 cycles) could be observed for
was recorded for MgCo2O4 nanowires grown on nickel foam as a LIB MgCo2O4 microparticles [165] synthesized using molten salt method
electrode [164]. The lack of binder in this direct growth method com proving the reduction of MgO layer through proper material synthesis
bined with a comparatively higher surface area (45.1 m2 g− 1) improved techniques.
Li+ transportation and improved cycling stability (~53%). Further research attempts to improve the porosity and the Lithium
Electrospinning method is considered an innovative method for storage in MgCo2O4 are still in progress. Recently porous nanoparticles
synthesizing one-dimensional nanomaterials such as nanowires, nano and nanosheets were synthesized by solvothermal [171] and
belts, and nanoribbons [179]. MgCo2O4 nanowires synthesized using microwave-assisted liquid phase method [172]. The SEM micrographs
electrospinning produced an appreciable surface area of 19.2 m2 g− 1 and (Fig. 8b) show the synthesized nanoparticles covered with porous
delivered a maximum capacity of ~600 mA h g− 1 at 0.24 A g− 1 [169]. nanostructures [171] showing improved intercalation sites for Li+
This capacity is lower than the nanowires produced by the hydrothermal obtaining an appreciable capacity of 935 mA h g− 1 (Fig. 9 a,b) and
method [164]; the binder included for the electrode preparation and its ~88% of capacitance retention after 150 cycles (Fig. 9 c,d). The assis
inferior surface area reduced its capacitance. However, the cycling sta tance of microwave improved the porosity of the MgCo2O4 nanosheets
bility of the material (~73%) is superior demonstrating lower evolution providing a higher capacity (1174 mA h g− 1 at 0.5 A g− 1) than its
of MgO during the cycling process proving the utility of nanowire theoretical capacitance and ~96% of capacitance retention after 100
morphology. Tailoring the porosity of MgCo2O4 material for improving charge-discharge cycles [172].
the Li intercalation process is gaining momentum recently. Fig. 8 shows MgCo2O4 based nanocomposites were also researched to improve
the XRD pattern, FESEM and TEM micrographs, elemental mapping of a their conductivity, solve SEI problems, and hence the cycling stability.
porous MgCo2O4 nanoparticle as an electrode for LIBs [171]. MgCo2O4/Li4Ti5O12 (LTO) composite was synthesized using a co-
The role of precipitating agents in modifying the porosity of precipitation technique; a two times improvement in the capacity of
MgCo2O4 nanocubes was investigated and determined that LiOH is an pristine LTO was observed [180]. However, the reversible capacity
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
achieved was ~300 mA h g− 1 and cycling stability of 85.5% after 150 5. Charge storability of MgCo2O4 as SCAP electrode
cycles. The composite’s capacity and stability were lower to other
MgCo2O4 nanostructures, but the activation sites and the conductivity For energy storage applications, light metals from the first four pe
of LTO improved with MgCo2O4 addition. Recent research modifying riods with large capacity are usually preferred [186] and Mg, along with
the surface of MgCo2O4 nanorods with TiO2 (MgCo2O4/TiO2 nano Co, belongs to a similar category. Various pseudocapacitive charge
composite) using oxalate decomposition technique improves the sta storage processes such as underpotential deposition, redox pseudoca
bility of SEI layer, inhibiting volume difference and further improving pacitance, and intercalation pseudocapacitance [111] were involved in
the conductivity along with structural and cycling stability [181]. This the charge storage materials such as RuO2, MnO2, etc. [187]. The earlier
composite provided a maximum reversible capacity of 856 mA h g− 1 research reported MgCo2O4 as a pseudocapacitive material citing
with superior cycling stability (~100%) after 300 charge-discharge cy intercalation pseudocapacitance [120]. However, its prominent redox
cles showing the higher stability of the SEI layer formed on the outer reaction [121] and the asymmetry of the charge-discharge area proved it
shell of TiO2. The Li intercalation to the TiO2 layer results in the for to be battery-type or SCAP material.
mation of LiXTiO2, which improves the conductivity and Li+ intercala The material’s SCAP utility is measured using a three-electrode
tion [182]. Although these research attempts to lower the MgO layer system as shown in Fig. 10, where the material pasted on nickel foam
formation and increase the Li ion storage in MgCo2O4 are progressing, or copper foil is measured against a reference electrode (usually Ag/
the material synthesis techniques discussed in these researches are un AgCl) along with the counter electrode (platinum wire). Fig. 10 also
able to synthesize large-scale MgCo2O4 porous nanostructures replacing comprises the schematics of the general charge storage process involved
graphite anodes. in supercapacitor electrodes. In SCAP, the charge storage process usually
Thus, the recent findings on the irreversible MgO formation in the involves redox chemistry of the materials; cation redox reaction causes
LIB electrode cites it as an advantage that avoids Mg2+/Mg reaction to energy storage in MgCo2O4 electrodes. The deep intercalation of OH−
Li+ intercalation [183]. MgO formed during the first charging process ions along with the Mg2+ and Co ions causes redox peaks in CV curves,
has high dissociation energy, thereby forming an SEI, which further demonstrating SCAP behaviour.
inhibits any volume variation in the electrode during the electro The energy storage process of MgCo2O4 as a SCAP electrode
chemical process [164]. Therefore, MgCo2O4 could be utilized as an involving cation redox reaction in the aqueous alkaline electrolyte, as
anode material solving the bulging thermal away. A research study has mentioned in Equation (1) [128]. The usual voltage window for the
also shown that the calcination temperature plays a crucial role in electrochemical measurements of the MgCo2O4 electrode is from 0 to
obtaining an additional MgO layer in MgCo2O4 that improves the charge 0.5 V (for typical alkaline electrolyte). A typical CV curve analyzed by
reversibility and capacity retention of LIBs [162]. We note the difference our research group for the MgCo2O4 electrode is given in Fig. 11; the
in these reported capacity values of MgCo2O4 electrodes could be redox pairs of Mg/MgO and CoOOH/Co(OH)2 fast reversible faradic
attributed to the preparation method, morphology, and, most impor reaction involved in the charge-discharge process can be observed as
tantly, normalization of the active material’s weight. Overall irre redox peaks. There is a change in the valence state of Co2+/Co3+ during
spective of particle size, morphology, and capacity, average discharge the electrochemical reaction [188]. The CV curve shows asymmetry
(~1V vs Li) and charge (~2V vs Li) voltage values of MgCo2O4 are between charge-discharge processes showing lower reversibility similar
higher than that of other well-known metal oxide anode (Li4Ti5O12) to batteries signifying it to be a SCAP electrode than a PC one.
(1.5V vs Li) [184] and intercalation graphite (0.25V vs Li) [185]. Furthermore, the redox peaks in CV curves [120,121] show that deeper
Therefore, future research can improve the voltage hysteresis and the surface intercalation of solvated ions resulting in a difference between
synthesis of appropriate morphology or composites involving MgCo2O4 charging and discharging areas providing areal capacitance than specific
using variable synthesizing techniques that emphasize material capacitance, thereby proving a SCAP charge process. Also, irreversible
scalability. 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
Fig. 10. Three electrode systems and schematics of the energy storage process in the MgCo2O4 electrode.
11
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
Fig. 11. A typical CV curve of MgCo2O4 electrode in the aqueous alkaline MgCo2O4 electrodes.
electrolyte at a scan rate of 60 mV s− 1. The first research attempt at exploring the supercapacitive perfor
mance of MgCo2O4 was performed by some of us [120], reporting the
practical capacitance, cycling stability, and the resistances (electrolyte, cause of CS is intercalation pseudocapacitance. Later, the redox peak in
electrode, and electrode-electrolyte) [188]. The voltage window is the the CV curves along with the variation in the instantaneous capacitance
property associated with the electrolyte and is termed as the potential in each interval prompted MgCo2O4 prompted researches to classify it as
window (V) available for the electrochemical process. The capacitance a SCAP material; the definition of the PC material was misinterpreted as
arises owing to the breaking of the chemical bond between the electrode such in many earlier reports [117]. Therefore, the CS of the MgCo2O4
materials due to electrolyte ion intercalation and the released energy electrodes as PC electrodes in alkaline electrolytes with clear redox
(electrical) will be stored as its capacitance [189]. Therefore, the elec peaks or non-linear potential decay should be reported in mA⋅h⋅g− 1 or in
trode material is equally important as of electrolyte. The energy stored C⋅g− 1 than F⋅g− 1. Table 5 comprises the research summary of different
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
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 improved CS (690 F g− 1; 96 mA h g− 1) and its cycling stability.
determined in F⋅g− 1 is converted to mA⋅h⋅g− 1 for future references. From A two-step hydrothermal synthesis and calcination technique suc
Table 5, one could observe that most of the recent researches in cessfully synthesized MgCo2O4 nanoneedles (Fig. 13e) on nickel foam
MgCo2O4 do not differentiate between PC and SCAP charge storage [194]. The BET surface area (25.6 m2 g− 1), average pore size diameter
proposing the necessity of having a benchmark to differentiate PC and (23.8 nm), and the pore volume (~0.17 cm3 g− 1) were ideal for elec
SCAP electrodes. trolyte (2 M KOH) ion intercalation. These physical properties of
Fig. 13 compiles the SEM micrographs or images of these materials. nanoneedles could produce a maximum CS of 804 F g− 1 and show
Morphology of electrode material could positively influence electron appreciable capacitance retention of 87.6% after 2000 cycles. The
transfer pathways, electrode-electrolyte contact area, and ion diffusion electrode resistance of the MgCo2O4 nanoneedles was lower (0.69 Ω)
lengths. The molten salt method was used to synthesize MgCo2O4 mi resulted in improved capacitance of the electrode. The lower resistance
croparticles (Fig. 13a) and explored its utility various electrolytes viz. of this electrode could be attributed to the combination of higher active
neutral and alkaline electrolytes; 3 M LiOH was determined to be the surface area, higher pore size diameter, and the binder-free electrode
best performing electrolyte [120]. The ‘V’ for the CD curve was 0.5 V fabrication technique. Although a similar binder-free hydrothermal
and the internal resistance of the electrode was also on the lower side fabrication technique is used for the aforementioned MgCo2O4 nano
(2.5 Ω). The particle agglomeration of microparticles lowers the BET cones with higher surface area (336 m2 g− 1) [128], the lower pore size
surface area (~0.45 m2 g− 1) shall block the electron pathways, thus diameter (7.8 nm) hindered the electrode conductivity lowering its
lowering the achieved CS signifying the role of morphology in the SCAP capacitance and cycling stability. Hence, the electrical conductivity of
electrode. The increasing CS in cycling stability (from ~80% to ~100% the electrode depends on the combination of higher surface, pore size
after 3000 cycles) suggests that the microparticle requires an activation diameter, morphology, and its redox state.
period to attain its maximum achievable capacitance. The porosity of the MgCo2O4 is further optimized using the reaction
Further, researchers synthesized various morphologies of MgCo2O4 time involved in the hydrothermal reaction [193]. The synthesized
using a hydrothermal method and used them for SCAP applications. The micro flower (Fig. 13f) consists of tiny nanosheets whose agglomeration
MgCo2O4 nanoneedle arrays (Fig. 13b) shown an improvement in the resulted in the formation of micro flowers further increasing its porosity.
BET surface area (~30 m2 g− 1); electrochemical studies in 2 M KOH The synthesized micro flowers provided a higher specific surface area
showed an improved voltage window (0.7 V) for CV curve; however, the (~72 m2 g− 1) together with pore size distribution ranging from ~21.7
CD curve demonstrated a voltage window of 0.5 V [197]. This varied nm to 150 nm; average pore diameter (~30 nm) was superior to other
voltage window for CV and CD curves is due to the potentiostat’s current mentioned morphologies. These conditions would have increased the
rating that depends on the mass loading of electrodes. Therefore, it is contact area between the electrode-electrolyte interface in addition to
advised to lower the electrodes’ mass loading for potentiostat with lower the active area utilization. However, the CS of the material was only 697
ampere ratings to avoid the difference in ‘V’ between CV and CD curves. F g− 1 (~97 mA h g− 1), showing that electrolyte ions do not fully utilize
The material’s porosity improved its CS owing to lower electrode resis the porosity, and also cycling stability was on the lower side (74.5%
tance (~1.5 Ω), showing a CS of ~508 F g− 1 in 2 M KOH at 2 A g− 1. after 5000 cycles).
Direct growth of MgCo2O4 nanocones (Fig. 13c) on nickel foam Three morphologies: nanosheet, nanobelt, and nanowire arrays
provides improved BET surface area (~336 m2 g− 1) proved to be elec (Fig. 13g) of MgCo2O4, were synthesized by changing the solvent com
trochemically active showing a CS of ~750 F g− 1 at 1 A g− 1 in 6 M KOH ponents on graphene-coated nickel foam. Nanowire arrays were
[128]. The MgCo2O4 porous nanocones on the nickel foam shorten the showing improved CS of 658 F g− 1 (~89 mA h g− 1) owing to its
pathways of electrons and electrolyte ions into the electrodes during the improved electron transport channel than the other two morphologies
charge-discharge process. However, similar to the earlier reports of [198]. The cycling stability of these nanowire electrodes was not
direct grown TMCs on nickel foam [200,201] cycling stability of the promising (~86% after 2000 cycles), proving the inferior cycling sta
electrode was inferior (~84% after 1000 cycles) at 1 A⋅g− 1 demon bility of structures grown on nickel foam; graphene-coated Ni-foam does
strating the limitation of the direct growth method for the practical not contribute to the stabilization of electrodes.
utility. A comparative study between the various spinel structure, MCo2O4
The effect of the processing parameters on the morphology (nano (M = Co, Mn, Fe, Mg, and Zn) microprisms for SCAP applications,
flowers and cuboidal microcrystals) of MgCo2O4 was studied by our determined the superiority of MgCo2O4 over other spinels in charge
group following the hydrothermal route [121]. The precursors for both storage [199]. The MgCo2O4 electrode shown an appreciable areal
the morphologies and reaction temperature (100 ◦ C) and duration (12 h) capacitance of 613.5 C g− 1 at 2 mA cm− 2. The improved performance is
were the same except the surfactants. Although the BET surface area of attributed to the combination of macro and mesoporous nature of the
nanoflowers (50 m2 g− 1) was higher than cuboidal microcrystals (18 m2 material, thus lowering the characteristic resistances, which credited to
g− 1) (Fig. 13d), the Mg content in cuboidal microcrystals determined the enhanced electrode-electrolyte ion transfer.
using Rietveld refinement of XRD was found to be higher. The stacked A recent research attempt synthesized MgCo2O4 nanoflake arrays,
morphology could easily facilitate ion transfer, thus showing an together with MgCo2O4/MgCo2O4 composite hierarchical nanostructure
13
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
(Fig. 13h) [196]. These structures were expected to improve electrical 5.1. MgCo2O4 composites
conductivity, higher redox activity, and higher charge storage proper
ties. The maximum specific capacitance for nanoflakes and hierarchical MgCo2O4 offers a higher theoretical CS and Table 5 shows that the
structures was ~317 mA h g− 1 and ~265 mA h g− 1, respectively. The maximum achieved CS is ~26% of it. The factors such as lack of elec
longer cycling stability of hierarchical structures was promising, trochemically active sites of the synthesized materials, lower porosity of
retaining ~98% at 6 A g− 1 after 5000 cycles. The utility of MgCo2O4 materials, and higher electrode resistance might have hindered in
nanoflakes with an appreciable mesopore diameter of ~12 nm was achieving higher capacitance. Therefore, research is focused on com
synthesized using hydrothermal synthesis [76]. The porous nature of the posites synthesis or modification of MgCo2O4 for SCAP applications to
material could explore a maximum capacitance of 734 F g− 1 (~88 mA h improve the stability and the CS.
g− 1) and provided a lower resistance (0.75 Ω) to the MgCo2O4 nanoneedles were deposited on silicon carbide flakes
electrode-electrolyte ion transfer which increased the achieved CS and (SiCF) with mesoporous and microporous nature having a higher spe
retaining ~95% of CS after 5000 cycles of continuous charge-discharge. cific surface area (1069 m2 g− 1) thereby combining both the EDLC and
It should be noted that the variation of hydrothermal temperature from SCAP property (MgCo2O4/SiCF nanocomposite) in a single electrode
120 ◦ C to 150 ◦ C retaining the similar experimental conditions and [202]. This combination has improved the ‘V’ to 0.6 V (1 M KOH) due to
precursors produced nanocubes having inferior pore size (~9.6 nm) the improvement in the electrochemical active sites as well as the
[76] and CS (~65 mA h g− 1). Therefore, the selection of temperature in electrical conducting channels of SiCF. Although there is an increase in
the hydrothermal method is important in synthesizing porous the composite’s surface area, the lower CS proves that the composite has
nanostructures. an increased EDLC behaviour than the battery type charge storage. Also,
Fig. 13 and Table 5 suggests that the morphology of the synthesized this proves that the surface area is not the only criteria to increase the CS
nano and microstructures of MgCo2O4 do not provide higher active of MgCo2O4; electrochemical characterization resulted in a CS of ~310
surface sites for the electrolyte ion intercalation. The BET surface area 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.
measurements of these materials measure a lower surface area ranging The stability of electrodes was promising compared to the pure elec
from 0.45 m2⋅g− 1 to 335.8 m2 g− 1. The extended intercalation (battery- trodes (~90% after 5000 cycles), proving that MgCo2O4 composites
type) capacitance depends on the pore size distribution and the pore could solve the stability issues.
volume of the electrode materials from Table 5, suggesting that the MgCo2O4 nanowires were fabricated at manganese dioxide nano
different morphologies of MgCo2O4 synthesized for SCAP electrodes flakes core-shell arrays were synthesized on graphene decorated nickel
consist of smaller pore size along with lower surface area. The materials’ foam (Fig. 14) and tested its utility for SCAP applications [203].
pore size distribution is also not ideal for the aqueous electrolyte Although the complex synthesis process involving chemical vapour
intercalation for SCAP energy storage as the pore size is much larger deposition and multiple hydrothermal syntheses is noncommercial, the
(more mesoporous pores than macropores). The hygroscopic nature of achieved capacitance is ~887 F g− 1 in 6 M KOH. This improvement
Mg hinders the broadening of surface ions and the surface agglomera could be attributed to the core-shell arrays for easy electrolytes as well
tion can be observed from the SEM images in Fig. 12. Also, the elec as electron transfer to the electrode pores. However, similar to the other
trochemical characterization was performed in alkaline electrolytes and direct grown materials on nickel foam, the electrode’s stability was not
the cycling stability of the material also needs improvement for material promising. It retained only about 87% of its initial capacitance at 10 A
commercialization. Therefore, future experiments could be designed to g− 1 at the end of 3000 cycles.
decrease the hygroscopic nature of Mg ions to synthesize 2D layered Critical performance analysis of MgCo2O4 as a SCAP electrode shows
structures with higher active surface areas as well as appropriate pore two prompt issues with its material synthesis and electrochemical
sizes. characterization. The absence of synthesis techniques such as
Fig. 14. Schematics of graphene coated MgCo2O4 fabricated on MnO2 core-shell arrays.
15
electrospinning, microwave-assisted hydrothermal method, etc. hin and higher power density (PS) of EDLC materials [206]. The flexible
dered the development of porous MgCo2O4 2D, 1D materials with uni ASCs will have ionic electrolytes or polymer electrolytes than the
form surface area and desired porosity. Adopting a suitable ratio of aqueous ones [207,208]. ASCs usually determine the energy and power
surfactant to fuel in the hydrothermal method with more optimization in density, demonstrating its energy and power capabilities. The ASC
reaction temperature could develop porous MgCo2O4 for SCAP appli fabrication involving MgCo2O4 as one of the electrode materials is
cations. Long term cycling or cycling stability was an issue for MgCo2O4 scarcely reported and most of the research work focuses on the
as well as its composites as a SCAP electrode. There are reports of an three-electrode system. The ASCs are fabricated, adopting a charge
increase in capacity even after 3000 CD cycles quoting the structural balance as q+=q- where q+ and q- are charges of positive and negative
activation time as the reason [204]. However, this problem may be due electrodes, respectively [65]. The general equation for a specific charge
to the formation of MgO during electrochemical reactions or due to the stored in both the electrodes is represented by equation (4).
dissolution of Mg in the electrolyte solution. Future researches could
qS = CS × ΔV × m (4)
explore these problems for the performance stability of MgCo2O4 as an
electrode for SCAP.
where the notations have their usual meaning, as discussed earlier. From
the above relation, the corresponding electrode mass requirement for
5.2. A solution to stability issues each electrode can be determined using equation (5)
m− CS+ (SCAP) × ΔV
The problem of low cycling stability of MgCo2O4 was investigated by = (5)
m+ CS− (EDLC) × ΔV
our research group [188]. Hierarchical MgCo2O4 nanostructures were
synthesized by the hydrothermal method. Its electrochemical studies Table 6 compiles the research progress of MgCo2O4 ASCs. An ASC
determined that the electrodes’ stability issue was caused by the Mg with MgCo2O4 nanosheets on Nickel foam as a positive electrode and AC
dissolution from the MgCo2O4 electrode into electrolyte after several as a negative electrode [195]. 6M KOH is used as an electrolyte for ASCs
charge-discharge cycles. Reduced graphene oxide (rGO) modified whereas 2M KOH for three-electrode studies; the increase in molarity of
MgCo2O4 were also synthesized and the electrochemical studies proved KOH could be for a higher voltage window (1.5 V) for the device.
that the Mg dissolution problem decreases with rGO modification of However, the maximum specific charge (Q) in the device at 0.5 A g− 1
MgCo2O4 electrodes [188]. A schematic representing the prevention of was determined to be 52 C g− 1 which is much lower than the Q (947 C
electrode material exfoliation owing to rGO modification is shown in g− 1) of MgCo2O4. Although, the ASC is fabricated calculating the active
Fig. 15. The variation in the CS cycling stability of MgCo2O4 at intervals area and maximum Q in each electrode; the lower Q of the device shows
of 5000 charge-discharge cyclings was stabilized using rGO modifica that an equal amount of charge transfer between the
tion. Therefore, future research can tailor the quantity of rGO and electrode-electrolyte interface does not occur [129]. The device’s
compare the stability as well as capacitance improvement in MgCo2O4. maximum energy density was determined to be ~13 W h kg− 1 at a
Also, rGO modification could improve the active surface area and the power density of ~449 W kg− 1, which is comparable with other TMC
porosity of MgCo2O4 to achieve a maximum capacitance closer to its ASCs.
theoretical value. Table 6 suggests that maximum research were performed to fabricate
different aqueous ASCs, employing MgCo2O4 as a positive electrode and
5.3. Asymmetric supercapacitor (ASC)/battery-supercapacitor hybrid AC as a negative electrode with various molar alkaline (KOH and LiOH)
(BSH) electrolytes. The energy density along with its cycling stability are the
important factors in determining the employability of these devices as a
An asymmetric supercapacitor (ASC) consists of either a pseudoca prototype and a commercial one. In these aqueous ASCs, a maximum ES
pacitive type/battery type electrode and an EDLC electrode, preferably of 39.7 W h⋅ kg− 1 is observed with higher cycling stability of 121.1%
activated carbon or mesoporous carbon [205]. The electrodes are after 5000 cycles [199]. A similar increase in capacitance after the
separated by a semi-permeable paper or separator soaked in electrolyte. cycling stability test can be observed for the other aqueous ASCs. This
Therefore, the ASC combines the properties of both the materials and improvement in cycling stability could be attributed to the structural
expected to combine higher energy density (ES) of the SCAP electrode activation of pores in the electrode material [65]. Usually, metal oxides
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
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 assumes that the entire electrode mass is electrochemically active for
supercapacitor electrodes. The commercially available EDLC has a cycle electron and ion intercalation, which is practically impossible. The
life of 103 to 105 cycles and has a higher voltage window of 2.7 V–3.0 V. electrode resistance, as well as charge transfer resistance, will be
Therefore, accepting the commercial capability of these aqueous ASCs is different for SCAP and EDLC materials. Therefore, the CV curves of these
possible only after a higher number of stability cycles. ASCs show an asymmetry in charge-discharge areas suggesting that the
For improving the cycling stability as well as voltage window of combination did not utilize the entire mass loading.
aqueous ASCs, Ni and Zn are co-doped with MgCo2O4. However, the ASC Research exploring a trial and error mass loading method compared
fabricated with the doped MgCo2O4 as cathode and AC as anode showed to the charge balance method in assembling an aqueous ASC using
improvement in ‘V’ (1.7 V) and ES (46.9 W h⋅ kg− 1), and the cycling MgCo2O4 and AC as electrodes [129]. MnCo2O4//AC were also fabri
stability of the device was inferior (76.4% after 20,000 cycles) [211]. cated as control devices. The research explored fabricating ASCs; ten
Similar lower cycling stability was observed for solid-state ASCs ASCs were fabricated varying the positive to negative electrode mass
employing PVA-KOH electrolytes [171,210]. In short, ASCs fabricated ratio out of which 1:1 mass ratio gives improved energy density of 31 W
using MgCo2O4 as a cathode provided appreciable energy densities h kg− 1 at a power density of 1.8 kW kg− 1 with 99% of cycling stability
compared to EDLCs. However, these energy densities were not superior after 3000 cycles at 5 A g− 1. The CV of the device (Fig. 16) with 1:1 mass
to other TMCs ASCs. Factors such as lower ion transport between the loading shows that the asymmetry and the charge storage are improved
electrode-electrolyte interface of the device, improper utilization of than the ASCs fabricated following the charge balance method. This
active surface area of the cathode and anode could be the reasons for its indicates that further optimization is required in EDLC as well as SCAP
inferior performances. Although the charge balance method of mass electrodes for ASC fabrication.
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 5.5. Dependence of electrolyte on the charge storage behaviour of
sues to improve their performance. MgCo2O4
Electrolyte (salt + solvent) contributing ionic conductivity, thereby

5.4. Exploring an alternate way of ASC mass loading allowing charge compensation on each electrode in supercapacitors
[213]. The EDL formation for carbon materials and the reversible redox
The ASCs were fabricated using a charge balance technique, reactions for SCAP or Battery-type as well as PC materials, will be
assuming that an equal number of charges will be stored in positive and influenced by the electrolytes [214]. The factors or characteristics of an
negative electrodes and a mass balance is required for it (Equation (4)). electrolyte such as ion size, solvent-ion interaction, solvent-ion con
Although Equation (4) proves to be theoretically correct, the proper centration (electrolyte molarity), electrolyte-electrode interaction,
electrochemical utilization of mass loading is doubtful. This Equation 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
[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
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 electrolytes, typically LiOH and KOH. However, the interaction between
lytes used for electrochemical characterization. electrode-electrolyte ions determines the intercalation mechanism of the
Besides, the H2/O2 evolution has occurred for microparticles in the electrode materials. Apart from this, the unsolved ionic size also affects
voltage range of ~0.45 V, whereas the hierarchical structures do not the SCAP charge storage. Researches prove that the charge storage
show this water decomposition of 3 M LiOH. The redox peaks seem to be mechanism of MnO2 improved with LiOH as an electrolyte than KOH
merged for the other CV curves, indicating ion intercalation variation to and citing the reason to be the small ionic radius of Li+ than K+ for easy
the electrode surface. Similarly, the CD curve also shows a variation in intercalation [218]. Similarly, reports of an increase in charge storage
potential drop (ΔV) for different structures proving the variation of are reported for NiO electrodes using NaOH electrolyte than KOH due to
resistance to electrolyte ions. Also, MgCo2O4 nanostructures mentioned the higher intercalation rate of Na+ than K+ [219]. Matching of pore
in Table 4 use KOH (2 M and 6 M) for the electrochemical character sizes of electrode material and electrolyte ions may improve the inter
ization. The variation in the energy storage process could be observed calation reaction, thereby improving the charge storage. Therefore,
from the CV and CD graphs (Fig. 19b–d, Fig. 20b–d). exploring various electrolytes matching the pore sizes of different
SCAP charge storage studies of MgCo2O4 is limited to two aqueous morphologies of MgCo2O4 as a SCAP electrode shall improve its
19
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. diffusion in cathodes. Although, with all these advantages, the two main
hindrances for MRB research are the synthesis of suitable cathode ma
6. MgCo2O4 as a cathode in magnesium rechargeable batteries terial for Mg2+ ion intercalation and the design of an appropriate elec
(MRBs) trolyte system [225]. Mg insertion demands a combination of high
electromotive force as well as high cation mobility for the cathode
The main disadvantage of LIBs is the safe deployment of metallic Li material [6,226]. Although oxide materials provide high electromotive
as an anode (negative electrode) due to the thermal runaway of Li after force, their higher activation energy of diffusion lowers the cation
several cycles of charge-discharge [220]. Replacement of metallic Li mobility [227]. However, this section is not exploring the cathode
with graphite, a material that can absorb Li+ ions at similar potential, (positive electrode) and electrolyte materials for MRBs but is limited to
results in a 10-fold decrease in the energy density of LIB [221]. Research the recent research prospects on developing MgCo2O4 as an MRB
on stabilization of Li metal anode developing suitable electrolyte addi cathode.
tives such as chlorosilanes, chloroboranes, and chlorophosphines enable The utility of MgCo2O4 synthesized using a reverse co-precipitation
a protective layer of Li surface to decrease thermal runaway is also in technique as a cathode for MIB is tested with Mg as an anode and Mg
progress [222]. The limited availability of lithium to certain countries (ClO4)2 as electrolyte [104]. The study assumed equation (6) for Mg2+
such as Australia, Chile, and Argentina, especially in 0.04–1.16% in intercalation.
brine ponds, and its longer duration for the synthesis of lithium car Mg1− x Co2 O4 + yMg2+ + 2ye →Mg1− (6)
x+y Co2 O4
bonate (~1 year) results in its increased cost [183]. Therefore, research
progressed further to determine alternate elements to replace lithium.
yMg → yMg2+ + 2ye
Sodium-ion batteries (SIBs) are one such investigated energy storage
devices replacing Li with Na [223]; however, a thermal runaway where x determines the number of earlier charges and y determines the
behaviour similar to LIB was also reported on SIB. number of discharge charges. This study presented the advantage of
Metallic Magnesium (Mg) demonstrated desirable electrochemical spinel MgCo2O4 for Mg2+ ion intercalation with a voltage window of 3.5
properties such as lower redox potential and lower reactivity (flamma V lighting a blue LED with a bandgap of 2.6 V. However, the solid-state
bility), thereby presenting as a candid anode material replacing Li metal diffusion process of Mg2+ions was lower, providing a lower energy
to form MRBs [224]. Furthermore, the earlier mentioned properties of density. Okamato et al. further validate the utility of MgCo2O4 as an
Mg, such as low cost and higher relative abundance, increase its electrode for MRBs, suggesting vacant 16c sites on which Mg cations can
advantage as an anode of the energy storage device. Also, the high be inserted, as shown in Fig. 21a [127]. Fig. 21b shows the significance
gravimetric (2205 mA h g− 1) and volumetric (3833 mA h cm− 3) of MgCo2O4 as a cathode for MRBs, showing its charge-discharge
capacitance of Mg compared to Li presenting its more suitability in capability at 1/10 C, showing a higher working potential after the 1st
portable electronic devices such as mobile phones over LIBs and NIBs discharge process (2–2.5 V vs Mg/Mg2+).
[225]. The lower standard electrode potential of Mg (− 2.4 V vs SHE) Additionally, the study has demonstrated that the MRBs prepared
along with the higher ionic radius of Mg2+ ions shall enable faster ion
20
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 Fig. 22c reveal the formation of spinel and rocksalt single phase and
insertion occurs at the higher potential of 2.9 V Vs Mg2+/Mg with the further insertion of Mg up to 210 mA h g− 1 transform it to single rocksalt
change in the valence state of Co(III) to Co(II) (Fig. 22a and b). Also, the phase. The XANES profile (Fig. 22 d) proves the reversible redox reac
study reveals that Mg insertion and extraction become more accessible tion of Co (III) cations in the spinel phase to Co (II) during the charge-
at elevated temperatures. This reaction mechanism is further studied discharge process at 120 mA h g− 1.
using XANES (X-ray absorption near edge spectroscopy). The XRD pro Sa et al. [167] further studied the Mg-intercalation mechanisms and
file after the discharge of 120 mA h g− 1 shows the presence of two both 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
scanning/transmission electron microscopy (S/TEM) to detect the resulting in a large overpotential for Mg dissolution [234–236]. Lately,
presence of amorphous MgO with crystalline MgCo2O4 materials, pre the modification of this electrolyte (Mg(TFSA)2) with MgCl2/triglyme
venting its long-term cycling. An intercalation-initiated surface con (G3) could suppress the overpotential of Mg dissolution, hence inhibit
version pathway is suggested for reducing amorphous MgO in the ing the passivation of Mg metal [237]. Further research on improving
interface. First-principle calculations were also made in substituting Mn the intercalation sites of Mg2+ in the MgCo2O4 spinel structure and
in MgCo2O4 (MgCo1.5Mn0.5O4) for its utility as MRB cathode; the reducing the MgO formation in the electrode-electrolyte interface shall
calculation and experiment prove that improved Mg insertion in contribute to developing a commercial MIB.
MgCo1.5Mn0.5O4 owing to weaker Mg–O bonds near Mn [228]. There
fore, selecting a suitable transition metal and substituting it in MgCo2O4 7. Conclusions
may improve the cycling stability of MgCo2O4 as a cathode for MRBs.
The transformation of spinel structure to rock salt structure of Thus, MgCo2O4 is a material with promising electrochemical prop
MgCo2O4 is validated using electron radiation from a scanning trans erties such as high theoretical charge storability, availability of a range
mission electron microscopy (S/TEM) [229]. These experiments, along of charge intercalation sites and oxidation states, and comparable
with first-order calculation, prove that the proposed intercalation-push electrical conductivity with many other electrochemical materials, for
out process of Mg ions into MgCo2O4 could be its reaction mechanism its potential deployment in energy storage devices. However, there are
of energy storage as MIB cathode. The schematics, along with SRTEM serious drawbacks, such as material stability under certain electrolytic
images of this crystal structure transformation is given in Fig. 23. It was conditions, formation of the inert layer during charge-discharge cycling,
determined that there is a small energy difference (39 meV) between the knowledge-gap on the materials’ physics, and cobalt oxide rarity. Our
Mg ions located at 8a sites and 16c sites owing to the transformation of analysis shows that several studies have been reported on the processing
spinel to rock salt structure. – property correlation with MgCo2O4 with a focus on developing diverse
The elevated temperature utility of MRB could facilitate improved morphologies and their property evaluation for lithium ion batteries,
intercalation of Mg2+ ions to the cathode material [127,230,231]. battery-supercapacitor hybrids, and magnesium ion batteries. Among
Moreover, Mg(TFSA)2 based electrolytes where TFSA stands for bis the only seven MgCo2O4 morphologies reported so far as a lithium ion
(trifluoromethanesulfonyl) could give appreciable cycling stability and battery electrode, few of them report higher lithium discharge capacity
charge storage at higher temperatures [232,233]. Nevertheless, the in the MgCo2O4 electrodes than the theoretical prediction. This provides
passivation of Mg- metal anode owing to the TFSA decomposition ample opportunities to explore this material with appropriate
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
substitution, doping, and defect structure tailoring as a cheaper elec electrolytes on carbon, proving that the carbon’s pseudocapaci
trode. Comparatively larger attempts were devoted to exploring the tive property could be increased [53]. Therefore, acetate elec
potential of MgCo2O4 as a battery-type electrode for battery- trolytes could also increase the redox reactions, thereby
supercapacitor hybrids. However, the eight MgCo2O4 morphologies re improving the energy storage capacity. The mixing of polymer
ported so far could show only up to ~26% of its theoretical capacitance; with the redox or acetate electrolytes could also help design
which, according to EIS studies, are due to higher electrode resistance flexible asymmetric supercapacitors with MgCo2O4 as a positive
and charge transfer resistance owing to its unoptimized surface and pore electrode. The stability of MgCo2O4 electrodes for SCAP appli
structure. Nevertheless, this large achievement gap between the lithium cations is an issue. However, the determination of an appropriate
ion storage capability and supercapacitive ion storage capability offers proportion of rGO addition to MgCo2O4 could improve its cycling
enormous opportunities to develop this material as a SCAP electrode stability.
through appropriate material modification. Although reports show (v) The practical applications of LIBs require the reduction of charge-
almost 100% achievement of capacity in the initial cycles, the inert MgO discharge voltages of MgCo2O4. The design of MgCo2O4 with a
layer formation considerably lowers the material’s recyclability. Recent proper pore size and employing the electrocatalytic technique
researches on magnesium rechargeable batteries (MRBs) determined could reduce the voltage. Full cell studies are required upon
desirable cathode properties for MgCo2O4. The main hindrance in reducing the voltage. Also, activating the higher valence state, i.
achieving the extended cycle life stability of MgCo2O4 in MRB is e., Co4+ of MgCo2O4 as observed in MRBs shall increase its
determining suitable electrolyte. Typically magnesium salt electrolytes voltage window, thus increasing its energy density. The explo
such as Mg(ClO4) and Mg(BF4)2 could passivate the transport of Mg2+ ration of dual salt batteries provides future utilities for MgCo2O4
ions forming surface films over Mg metal. The development of new as a cathode material.
electrolytes could improve the performance of MgCo2O4 as a cathode for (vi) The recent development in designing an efficient Na–Mg battery
MRBs. where anode and cathode were metallic Mg, and FeS2, respec
tively, with Na/Mg dual salt electrolyte [221]. However, this
8. Recommendations 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
We have the following recommendations for developing this mate energy density. A Li–Mg dual salt battery is also proposed with
rial for its practical deployability from the critical analysis embodied in MgCo2O4 as cathode material and an ionic liquid electrolyte for
this article on the charge storability in the MgCo2O4 electrode. both Li and Mg insertion with a voltage window of ~3V [101].
Future research in improving the energy density and commer
(i) Adopting a suitable surfactant during synthesis and optimizing cialization of these dual batteries shall accommodate MgCo2O4 as
the reaction temperature, the agglomeration of nanoparticles its cathode material for “intercalation and push-out” processes.
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 Declaration of competing interest
age capabilities of MgCo2O4. Few important aspects still missing
on the synthesis of MgCo2O4 are (a) thorough processing – The authors declare that they have no known competing financial
property correlation, (b) distribution of cation (either random or interests or personal relationships that could have appeared to influence
ordered) in the material and understanding their role in deter the work reported in this paper.
mining the final morphology, and (c) a through structure-
property correlation as a function of cation distribution aimed Acknowledgments
to understand the best charge storage conditions in MgCo2O4
electrode. This understanding would help identify the conditions The authors would like to acknowledge the research fundings
for the synthesis of the 1D morphology of MgCo2O4 such as through Research Center Grant Scheme 2019 (STR-RCTR-GAMRG-001-
nanowires and nanorods, which are shown to be superior for 2019), Collaborative Research Fund (STR-RMF-MRU-001-2019), and
charge storability due to improved electrolyte-electrode ion/ Fundamental research grant scheme of the Ministry of Higher Educa
electron transportation as well as anisotropic charge movement tion, Malaysia (FRGS/1/2019/STG07/UMP/01/1). The authors also
in the electrode. thank Dr. Anju V. Nair, for her valuable inputs in the manuscript.
(ii) Material modification of cobalt oxide with appropriate substitu
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Renewable and Sustainable Energy Reviews 141 (2021) 110798

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Energy storage in metal cobaltite electrodes: Opportunities & challenges in

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

Abbreviations Ni(OH)2 Nickel hydroxide

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

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

in the SCAP electrodes is evaluated by three processes viz. cyclic vol

Electrolyte (salt + solvent) contributing ionic conductivity, thereby

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

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

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1 s2.0 S1364032121000939 Main

Uploaded by

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1 s2.0 S1364032121000939 Main

Uploaded by

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Copyright

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1 s2.0 S1364032121000939 Main

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Renewable and Sustainable Energy Reviews 141 (2021) 110798

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Energy storage in metal cobaltite electrodes: Opportunities & challenges in

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

Abbreviations Ni(OH)2 Nickel hydroxide

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

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

in the SCAP electrodes is evaluated by three processes viz. cyclic vol­

Electrolyte (salt + solvent) contributing ionic conductivity, thereby

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

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

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in the SCAP electrodes is evaluated by three processes viz. cyclic vol