As lithium-ion batteries approach their theoretical limits for energy density, magnesium-ion batteries are emerging as a promising next-generation energy storage technology. However, progress in magnesium-ion battery research has been stymied by a lack of available high capacity cathode materials that can reversibly insert magnesium ions. Vanadium Oxide (V2O5) has emerged as one of the more promising candidate cathode materials, owing to its high theoretical capacity, facile synthesis methods, and relatively high operating voltage. This review focuses on the outlook of hydrated V2O5 structures as a high capacity cathode material for magnesium-ion batteries. In general, V2O5 structures exhibit poor experimental capacity for magnesium-ion insertion due to sluggish magnesium-ion insertion kinetics and poor electronic conductivity. However, several decades ago, it was discovered that the addition of water to organic electrolytes significantly improves magnesium-ion insertion into V2O5. This review clarifies the various mechanisms that have been used to explain this observation, from charge shielding to proton insertion, and offers an alternative explanation that examines the possible role of structural hydroxyl groups on the V2O5 surface. While the mechanism still needs to be further studied, this discovery fueled new research into V2O5 electrodes that incorporate water directly as a structural element. The most promising of these hydrated V2O5 materials, many of which incorporate conductive additives, nanostructured architectures, and thin film morphologies, are discussed. Ultimately, however, these hydrated V2O5 structures still face a significant barrier to potential applications in magnesium-ion batteries. During full cell electrochemical cycling, these hydrated structures tend to leach water into the electrolyte and passivate the surface of the magnesium anode, leading to poor cycle life and low capacity retention. Recently, some promising strides have been made to remedy this problem, including the use of artificial solid electrolyte interphase layers as an anode protection scheme, but a call to action for more anode protection strategies that are compatible with trace water and magnesium metal is required.

In recent years there has been some discrepancy about whether crystalline or amorphous V 2 O 5 is the superior cathode material for magnesium-ion batteries, with many publications suggesting that amorphous V 2 O 5 more readily stores magnesium ions. In this work, we report the systematic investigation of magnesium ion storage in crystalline and amorphous V 2 O 5 electrodeposited thin films. Our results indicate that the electrochemical performance of V 2 O 5 thin films is primarily impacted by the presence of adsorbed water. This study finds that the adsorbed water left over from aqueous electrodeposition is mostly responsible for the observed improved performance of amorphous V 2 O 5 thin films, thereby indicating that the drying conditions, rather than the crystal structure, play a direct role in enhancing the electrochemical performance. We propose an explanation for this observation in that the amorphous thin film has much larger water content, leading to increased interlayer spacing within the disordered structure and possible charge shielding for magnesium-ion storage. Ultimately, this study demonstrates the importance of considering the effect of adsorbed water, especially when comparing the electrochemical performance of amorphous and crystalline V 2 O 5 synthesized from wet electrodeposition techniques.

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The PMo₁₂-PPy heterogeneous cathode was synthesized electrochemically. In doing so, the PMo₁₂ redox-active material was impregnated throughout the conductive polymer matrix of the poly(pyrrole) nanowires. All chemicals and reagents used were purchased from Sigma-Aldrich. Anodized aluminum oxide (AAO) purchased from Whatman served as the porous hard template for nanowire deposition. A thin layer of gold of approximately 200nm was sputtered onto the disordered side of the AAO membrane to serve as the current collector. Copper tape was connected to the sputtered gold for contact and the device was sealed in parafilm with heat with an exposed area of 0.32 cm² to serve as the electroactive area for deposition. All electrochemical synthesis and experiments were conducted using a Bio-Logic MPG2 potentiostat. The deposition was carried out using a 3-electrode beaker cell setup with a solution of acetonitrile containing 5mM and 14mM of the phosphomolybdic acid and pyrrole monomer, respectively. The synthesis was achieved using chronoamperometry to apply a constant voltage of 0.8V vs. Ag/AgCl (BASi) to oxidatively polymerize the pyrrole monomer to poly(pyrrole). To prevent the POM from chemically polymerizing the pyrrole, an injection method was used in which the pyrrole monomer was added to the POM solution only after the deposition voltage had already been applied. The deposition was well controlled by limiting the amount of charge transferred to 300mC. Following deposition, the AAO template was removed by soaking in 3M sodium hydroxide (NaOH) for 20 minutes and rinsed several times with water. After synthesis, all cathodes underwent electrochemical testing to determine their performance using cyclic voltammetry and constant current charge-discharge cycling in 0.1 M Mg(ClO₄)₂/PC electrolyte. The cathodes were further characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), and x-ray photoelectron spectroscopy (XPS).

As global energy demands continue to rise each year, current state-of-the-art Li-ion battery (LIB) systems are predicted to reach the limit in the amount of energy that they can supply. In addition to this, LIBs are also limited by the low resource availability of Li metal. One proposed solution is to move away from LIBs to multivalent ion systems; of these alternatives, magnesium (Mg) is considered a promising material for the next generation of rechargeable batteries. Unlike Li, Mg metal does not form dendritic structures during cycling which would allow it to be employed as an anode which has a specific capacity of 2205 mAh/g compared to 777 mAh/g of the graphite anode that is currently used in LIBs. Mg also has a very high elemental abundance in the earth’s crust (2.44x104 ppm) which would drive down the production cost while simultaneously ensuring the longevity of these batteries in terms resource availability. Most importantly, the divalent nature of the Mg-ion means that it can carry twice the amount of charge per ion compared to Li. This is largely related to the high volumetric capacity (3833 mAh/ml) of Mg which is superior to even that of Li metal. While there is potential for Mg to replace LIBs, commercialization of these batteries has been hindered by sluggish insertion kinetics into cathode host materials as a direct result of the strong coulombic interactions experienced by the divalent Mg-ion. Due to this drawback, conventional metal oxide or sulfide insertion cathodes for Mg batteries tend to exhibit low capacities and operating voltages. In response to this, a large portion of Mg battery research is currently focused on the development of novel materials capable of functioning as cathodes for fast and efficient Mg-ion insertion. The idea proposed in this work is to depart from the conventional intercalation mechanism of LIBs and move towards a molecular cluster battery (MCB) based on polyoxometalate (POM) metal oxygen cluster molecules of early transition metals (Mo, W, V, or Nb). The unique redox activity of POMs are due to their intrinsic ability to form highly stable reduced and oxidized species allowing them to partake in fast reversible electron transfer reactions. Although POMs are also able to function as electron reservoirs, POMs themselves have negligible electronic conductivity as well as high solubility in both aqueous and organic media. Therefore, in order for these materials to be used as electrodes for electrochemical energy storage, they must first undergo hybridization with highly conductive insoluble substrates such as conductive organic polymers (COPs) or multi-walled carbon nanotubes (MWCNTs). The fabrication of heterogenous cathodes provide a “wiring” effect by electrically connecting the POM molecules allowing them all to take part in the redox chemistry while simultaneously anchoring them to a substrate, thus preventing any loss of active material to electrolyte dissolution during cycling. By taking advantage of the synergistic effect of pairing the ionically conductive POM molecule with the electrically conductive substrate; the resulting cathode material will thus be capable of fast electron transfer reactions with high ionic mobility. In this work, hybrid nanostructured electrodes of poly-3,4-ethylenedioxythiophene (PEDOT) and a phosphomolybdic acid (H3PMo12O40) POM have been fabricated electrochemically and applied as cathodes for Mg-ion storage. Preliminary cyclic voltammetry and galvanostatic cycling data have demonstrated an enhancement in the capacity of the PEDOT cathode after integration of the POM molecules throughout the polymer matrix. The initial cycling studies have also shown that the PEDOT-POM redox peaks are still present after 7 days of soaking in the organic electrolyte which suggests that the POM molecules do not readily dissolve out of the PEDOT matrix. This work highlights the potential of redox active POM inorganic clusters to function as cathodes with the capability of advancing the current state of Mg batteries.