A new cathode used in magnesium-ion batteries

Rechargeable Mg+2 ion batteries, post-Li+1 ion batteries, are aimed at providing several

advantages, like great safety features, high sustainability, cost effectiveness, and high energy.

Although magnesium electrolytes have developed in recent years, their steady growth is hindered

by a lack of suitable cathode materials, primarily owing to the high charge density of magnesium

ions' and kinetic limit. Nanostructured cathode materials, Ni-doped magnesium manganese oxide

as the cathode, and reversible insertion of Mg-ions into nanostructured conversion-type CuS

cathodes are the options among the variety of cathodes used in magnesium batteries. The cathode

materials provide an effective way to lessen these difficulties because of their longer diffusion

times and larger surface areas. We now introduce the highly reversible insertion of ions into a

nanostructured CuS cathode of the conversion type, yielding high capacities of 300 mAh g−1 at

ambient temperature and

Introduction

Magnesium batteries offer several advantages over commercial lithium batteries,

including a predicted lower cost due to the greater abundance of Mg and better theoretical

performance [1]. Currently, there are numerous challenges to overcome in delivering commercial

Mg batteries, such as the high charge density of Mg2+ that hinders its intercalation in and out of

the cathode or strict requirements for coordination of Mg2+[2-4]. Rechargeable batteries are

energy-efficient systems and are needed in the modern world due to the greater demand for

renewable energy[5, 6]. All state-of-the art technologies are in search of more energy-acquisition

options. Among other global challenges, rechargeable batteries for long-range vehicles have

gained importance. Still, lithium-ion batteries are a major contributor, accounting for 350–700
WL/h of the energy density, but another intriguing contributor is magnesium, which is

abundantly found in the earth's crust and lighter than other elements. Divalent mg has a great

volumetric energy density, almost double the lithium ions, making them a credible lithium

alternate for next-generation storage systems [7].

Dendrites are formed by using liquid electrolytes with Na or Li batteries, while no

dendrites are formed, surprisingly, with mg. But the major obstacle to commercialising Mg is

slower solid-state ionic diffusion. A number of intercalation agents, like phosphates, sulphides,

and oxides, are reported to contribute to the energy density of magnesium [8]. Inorganic and

organic cathodes both offer their specific advantages. The development of organic cathode

materials has made them less toxic and have a high theoretical capacity for Mg batteries[2, 9].

Strategies and experimentation for the preparation of cathode materials for magnesium-

ion batteries

A rechargeable Mg-ion battery is comprised of an electrolyte in which electrolysis takes

place and two electrodes. Anode is either Mg metal or Mg alloy, and cathode is either inorganic

(metal sulphide, phosphate, or oxide) or organic (sulphur, nitrogen, or carbonyl-based)[10, 11].

During discharging, the anode releases electrons and Mg ions in the electrolyte, while the

cathode receives Mg ions. Oxidation takes place at the Mg anode and reduction at the cathode,

and electrons flow from a higher potential towards a lower potential. In such batteries, the

cathode material must show a high redox reaction, irrespective of whether it is organic or

inorganic[12]. Transition metals like Mn, Ni, W, Fe, Cu, and V are key components among the

inorganic components of cathodes while some organic compounds are more advantageous in

terms of theoretical capacity, safety, and sustainability[13].

1: Vat Orange 11—Based Organic Cathode Material

Carbonyl-conjugates offer more structural diversity, volume, and charge density. Vat

orange dye was recently used in a study, as a cathode material for an APC-based electrolyte for

secondary, non-aqeous electrolyte. The performance of the vat orange was analysed in different

electrolytes like Ph-mg-Cl-AlCl3, APC-LiCl, and MMTP TFSI, which demonstrated excellent

performance and a long cycle. It happened due to the suspension of the dissolution of VAT

orange in the electrolyte, which led to enhanced stability and electrochemical performance. The

study also investigated the pathway of Mg ion uptake by FTIR analysis. Analysis showed the

magnesiation and demagnesiation processes take place due to the transformation of the carbonyl

to the enole group. The carbonyl double bond is converted into a single bond through resonance.

In the charging process, the C=O and C=C regain their positions. The results proved that organic

compounds could be a promising candidate for cathode in Mg-ion-based batteries [14, 15].

2: Ni-doped magnesium manganese oxide as a cathode

Another study [16] revealed the use of nickel-doped todorokite (Nix,-Mg-I) for the

cathode material used in Mg batteries. Major advantages of using this cathode include increased

conductivity and ion balance, excellent electrochemical performance, and suppression of the

Jahn-Teller effect. It showed great cycle performance in the Mg(NO3)2 electrolyte, and after 300

cycles, it had a retention rate of 89.7%, proving its potential as a cathode material to be used in

magnesium batteries. In the same study, the VO2 Nano rod was analyzed for its electrochemical

performance in magnesium-ion batteries. It showed a good rate property, capacity of discharge at

different current densities, and high retention after several cycles of charging. Various analysis

techniques, like XRD, TEM, and SEM, were used for detailed imaging. VO2 indicated high
crystallinity. SEM and TEM showed detailed morphology and proved that its Nano size is

suitable for insertion and deinsertion [17]. Some of the major challenges in magnesium-ion

batteries with such cathodes are the formation of MgO from traces of moisture content. Lack of

any proper electrolyte is another problem in the development of the Mg batteries[18, 19].

3: Copper sulfide nanoparticles as high-performance cathode

In another sudy [20, 21] it was reported copper sulphide nanoparticles as new cathode

materials for Mg-ion storage and a plausible stategy is formation of nano structures for cathode.

The particles exhibited higher capacity of approximately 300mAh -1g at a density of 1000 mAg -

1. Further it remained stable over 200 cycles. Magnesiation and demagnesiation mechanism was

studied by XPS and EDX. But it is associated with a problem of enhanced formation of solid

electrolyte interface due to high surface area. Some recent examples of Nano structured Mg

cathode are MoS2, TiS, VOx, and conformable V2O5. All of them are proven now for their

energy efficiency and higher capacities. Bulk cathodes often allow magnesiation at elevated

temperatures. CuS offers one of the highest available capacities at 560 mAh g−1 and has a high

electrical conductivity of 103 S cm−1 39–47. Te CuS conversion electrodes reported to date,

however, suffered from reduced rate capabilities and cycling stabilities at room temperature,

which is associated with the large structural reconstruction of the electrodes during cycling. Tis

leads to large volume changes and thus destruction of the electrodes. Specifically, up to recently,

the best cycling stability tests for CuS cathodes at room temperature showed a rather low

gravimetric capacity of 153 mAh g−1 after 20 cycles, with a low capacity retention of 75% and a

large voltage hysteresis, resulting in a poor energy efficiency of 68%. It was reported on CuS

NPs as cathodes for Mg-ion batteries, using commercial 90–150nm CuS NPs and achieved a

high charge-storage capacity of 175 mAh g−1 at a current density of 50mAg−1 [22]. In this
context, Nano structuring and the formulation of suitable sof composites could be an effective

way to accommodate large structural changes in conversion-type cathode materials and enhance

the kinetics of the electrochemical conversation reactions[23]. Nanostructured CuS in the form

of 20nm nanoparticles (NPs) delivers at room temperature a high capacity of 300 mAh g−1 at a

current density of 100mAg−1 , outperforming its bulk counterparts. Bulk CuS showed negligible

electrochemical activity at room temperature, which improved only at an elevated temperature of

50 °C. A side-by-side comparison of nano and bulk CuS showed that the electrochemical

performance of bulk CuS is only comparable with that of nano CuS at an elevated temperature of

its performance was negligible at room temperature. Concluding that nanostructuring is an

effective approach to overcome kinetic limitations of conversion-type copper (II) sulfide

cathodes that are observed in the bulk system[21].

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