Electrodeposition of Vanadium Oxide/Manganese Oxide Hybrid Thin Films on Nanostructured Aluminum Substrates

Abstract

Electrodeposition of functional coatings on aluminum electrodes in aqueous solutions often is impeded by the corrosion of aluminum. In the present work it is demonstrated that electrodeposition of vanadium oxide films on nanostructured aluminum substrates can be achieved in acidic electrolytes employing a novel strategy in which a thin interspacing layer of manganese oxide is first electrodeposited on aluminum microrod substrates. Such deposited films, which were studied using SEM, XPS, XRD, and surface enhances Raman scattering as well as chronopotentiometry, are shown to comprise a mixture of vanadium oxidation states (i.e. IV and V). As this all-electrochemical approach circumvents the problems associated with aluminum corrosion, the approach provides new possibilities for the electrochemical coating of nanostructured Al substrates with functional layers of metal oxides. The latter significantly facilitates the development of new procedures for the manufacturing of three-dimensional aluminum based electrodes for lithium ion microbatteries. The continuous miniaturization within the field of electronics has created increased interest in the modification of nanostructured substrates and electrodeposition has emerged as a particularly promising technique for straightforward and cost-effective preparation of threedimensional (3D) structures, allowing the realization of nanostructures with functional layers.1,2 The fact that the fabrication and coating of complex 3D nanostructures can be carried out at low temperatures with precise control differentiates electrochemical deposition from other thin film deposition techniques including physical vapor deposition (PVD), chemical vapor deposition (CVD) and atomic layer deposition (ALD).1 Template-assisted electrodeposition has been demonstrated to be a particularly versatile technique in the manufacture of nanostructured substrates, such as 3D arrays of copper 3,4 and aluminum nanorods. 5,6 Whereas the deposition of copper nanostructures is relatively straightforward, the corresponding deposition of aluminum nanostructures is more demanding 1 due to the need for non-aqueous solutions and a controlled oxygen-free atmosphere. Electrochemical deposition of layers of functional material on aluminum from aqueous solutions is further complicated by the fact that the aluminum surface is coated by a passivating Al 2 O 3 film between pH 5 and 8, while there is aluminum corrosion in acidic as well as alkaline solutions. 7Aluminum has a wide field of application mainly due to its low cost, low weight and high thermal and electronic conductivities.8 Much work has therefore been carried out to develop techniques for the protection of Al surfaces from corrosion, e.g. based on electrodeposition of protecting polymer layers on planar aluminum substrates. [8][9][10] In addition, a significant interest in investigating the possibilities for electrodeposition of electroactive layers on aluminum nanostructures has recently arisen as a result of the success in the manufacturing of electrodep...

3D Vanadium Oxide Inverse Opal Growth by Electrodeposition

“…[10][11][12][13] Electrodeposition is a particularly facile route for the formation of metal and metal oxide films on a variety of conductive substrates and has recently gained a lot of attention for synthesising three-dimensional materials when combined with templates and sacrificial architecture-directing structures. [14][15][16][17] Vanadium pentoxide is a particularly attractive replacement cathode material with its mixed valence, V 4+ and V 5+ , making it an ideal candidate for a large number of redox-dependent applications. Vanadium pentoxide (V 2 O 5 ) can be synthesized by a number of techniques, including hydrothermal synthesis, 18,19 sol-gel techniques, 20 chemical vapor deposition, and atomic layer deposition.…”

The Influence of Colloidal Opal Template and Substrate Type on 3D Macroporous Single and Binary Vanadium Oxide Inverse Opal Electrodeposition

“…IO electrodeposition is similar for both substrates at 2.0 V and consistently produced higher quality IO structures, defined internal wall structure and is diffusion limited growth which ensures continual growth of V 2 O 5 throughout the interstitial voids of the opal template. Negligible current and IO growth is found at redox potentials of V 4+ /V 5+ in aqueous solution, where, as Rehnlund 45 discusses, V 2 O 5 precipitates from more V 5+ content formed at higher potentials. The chronoamperograms in Fig.…”

“…along with different materials, 29,[39][40][41][42][43][44] further highlighting the versatility of this approach. 25,45,46 However, very few systematic investigations on the factors influencing IO formation using ED (i.e. impact of sphere template, ED voltage and time, choice of substrate etc.)…”

Electrolytic Manganese Dioxide Coatings on High Aspect Ratio Micro-Pillar Arrays for 3D Thin Film Lithium Ion Batteries

“…Several methods for 3D electrodes manufacturing have been reported in the literature [ 7 , 8 , 9 , 11 , 12 ]. Silicon (Si) is widely used as processing material for electronic devices integration [ 13 , 14 ].…”

“…Nanowire arrays and nanorods have been also detailed showing an improvement in electrode performance due to the current collector geometries as well as the deposited active materials like Cu 2 Sb, Fe 2 O 3 and TiO 2 [ 7 , 24 , 25 , 26 , 27 ]. Such materials can be prepared by a variety of techniques such as electrochemical deposition (ECD) [ 12 , 28 ] , atomic layer deposition (ALD) [ 29 , 30 ], chemical vapor deposition (CVD) [ 31 ], and sol-gel deposition [ 9 ]. For 3D current collectors, the deposition of a conformal coating is challenging.…”