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Ultrathin nanosheet-assembled cobalt molybdate (CoMoO4) with a mesoporous morphology was synthesized by a urea-assisted solution combustion route at a temperature of 400 °C.

Scheme 1 Low acidic and neutral solutions. Scheme 2 High acidic solutions.This journal is

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. amorphous NiPO 4 and a minor product of nickel (II) hydroxide (β-NiOOH). During subsequent reduction, lithium ions are not fully intercalated, however, the structure is reversible and adequate for multiple cycles. The high potential in LiNiPO 4 looks to be very attractive in terms of high energy density, given the efficiency is improved.

The effect of zinc (Zn) doping and defect formation on the surface of nickel molybdate (NiMoO 4 ) structures with varying Zn content has been studied to produce one-dimensional electrodes and catalysts for electrochemical energy storage and ethanol oxidation, respectively. Zn-doped nickel molybdate (Ni 1-x Zn x MoO 4 , where x = 0.1, 0.2, 0.4, and 0.6) nanorods were synthesized by a simple wet chemical route. The optimal amount of Zn is found to be around 0.25 above which the NiMoO 4 becomes unstable, resulting in poor electrochemical activity. This result agrees with our density functional theory calculations in which the thermodynamic stability reveals that Ni 1-x Zn x MoO 4 crystallized in the β-NiMoO 4 phase and is found to be stable for x≤0.25. Analytical techniques show direct evidence of the presence of Zn in the NiMoO 4 nanorods, which subtly alter the electrocatalytic activity. Compared with pristine NiMoO 4 , Zn-doped NiMoO 4 with the optimized Zn content was tested as an electrode for an asymmetric supercapacitor and demonstrated an enhanced specific capacitance of 122 F g −1 with a high specific energy density of 43 W h kg −1 at a high power density of 384 W kg −1 . Our calculations suggest that the good conductivity from Zn doping is attributed to the formation of excess oxygen vacancies and dopants play an important role in enhancing the charge transfer between the surface and OH − ions from the electrolyte. We report electrochemical testing, material characterization, and computational insights and demonstrate that the appropriate amount of Zn in NiMoO 4 can improve the storage capacity (∼15%) due to oxygen vacancy interactions.

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The race for better electrochemical energy storage systems has prompted examination of the stability in the molybdate framework (MMoO; M = Mn, Co, or Ni) based on a range of transition metal cations from both computational and experimental approaches. Molybdate materials synthesized with controlled nanoscale morphologies (such as nanorods, agglomerated nanostructures, and nanoneedles for Mn, Co, and Ni elements, respectively) have been used as a cathode in hybrid energy storage systems. The computational and experimental data confirms that the MnMoO crystallized in β-form with α-MnMoO type whereas Co and Ni cations crystallized in α-form with α-CoMoO type structure. Among the various transition metal cations studied, hybrid device comprising NiMoO vs activated carbon exhibited excellent electrochemical performance having the specific capacitance 82 F g at a current density of 0.1 A g but the cycling stability needed to be significantly improved. The specific capacitance of the NiMoO electrode material is shown to be directly related to the surface area of the electrode/electrolyte interface, but the CoMoO and MnMoO favored a bulk formation that could be suitable for structural stability. The useful insights from the electronic structure analysis and effective mass have been provided to demonstrate the role of cations in the molybdate structure and its influence in electrochemical energy storage. With improved cycling stability, NiMoO can be suitable for renewable energy storage. Overall, this study will enable the development of next generation molybdate materials with multiple cation substitution resulting in better cycling stability and higher specific capacitance.

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