Alloys comprising aluminum (Al) and one or more transition metals (TMs) exhibit excellent physical and mechanical properties. Among the various transition metals with which Al can be alloyed, nickel (Ni) is particularly interesting because Al—Ni alloys exhibit excellent corrosion resistance, high temperature oxidation resistance, high strength, good ductility, and magnetic pertinence. In addition to Al—Ni alloys, Al/Ni multilayer structures that comprise alternate layers of Al and Ni are of interest because such structures also exhibit many desirable properties, including easy ignition, self-sustaining exothermic synthesis after reaction, high local temperatures upon propagation (around 1000° C.), and zero emission.
Various processing techniques have been used to synthesize Al—Ni alloys and Al/Ni multilayer structures, including physical vapor deposition (PVD), plasma-assisted chemical vapor deposition (PACVD), hot pressing, and electromagnetic stirring. Not included in this list, however, is electrodeposition. The reason for this is that it is difficult to form Al—Ni alloys and Al/Ni multilayer structures through electrodeposition using a single electrolyte solution. Conventionally, electrodeposition of Ni is performed using an aqueous solution at or near room temperature, while electrodeposition of Al is typically performed using a molten salt electrolyte at high temperature (e.g., ˜1000° C.). It is unfortunate that a suitable electrodeposition technique has not been developed for these metal systems because electrodeposition is more economical and easier to scale as compared to the other techniques that have been used. In addition, electrodeposition enables one to easily control the composition and phase of the deposit through adjustment of the deposition parameters, including electrolyte composition, agitation, temperature, and current/potential.
In view of the above discussion, it can be appreciated that it would be desirable to be able to form Al—Ni alloys and/or Al/Ni multilayer structures through electrodeposition.
The present disclosure may be better understood with reference to the following figures. Matching reference numerals designate corresponding parts throughout the figures, which are not necessarily drawn to scale.
As described above, it would be desirable to be able to form aluminum-nickel (Al—Ni) alloys and/or aluminum/nickel (Al/Ni) multilayer structures through electrodeposition. Disclosed herein are methods for forming such alloys and structures through electrodeposition using a single electrolyte solution. In some embodiments, Al—Ni alloys are electrodeposited at room temperature using an electrolyte comprising a solution of aluminum chloride (AlCl3), nickel chloride (NiCl2), and an organic halide. In some embodiments, Al/Ni multilayer structures are formed by first depositing Ni and then depositing Al on the nickel using a single electrolyte solution comprising AlCl3, NiCl2, and a an organic halide. In some embodiments, the organic halide can be selected from the group consisting of 1-ethyl-3-methylimidazolium chloride (EMIM), N-[n-Butyl] pyridinium chloride (BPC), and trimethylphenylammonium chloride (TMPAC).
In the following disclosure, various specific embodiments are described. It is to be understood that those embodiments are example implementations of the disclosed inventions and that alternative embodiments are possible. All such embodiments are intended to fall within the scope of this disclosure.
Electrodeposition in non-aqueous room-temperature solutions or ionic liquids provides a cost-effective alternative to fabricating Al alloys and multilayer structures. As used herein, the term “multilayer structure” is used to describe any structure comprising multiple alternating layers of materials, including “bilayer” structures that comprise two alternate layers of material and structures that comprise three or more layers of alternating material. Room temperature ionic liquids synthesized by adding AlCl3 to an organic halide provides useful and attractive characteristics, such as adjustable Lewis acidity, wide electrochemical window, aprotic nature, room-temperature stability, good conductivity, and low vapor pressure. AlCl4− and Al2Cl7− unsaturated species are present in the electrolyte while the concentration of the latter increases with electrolyte acidity. The acid-base characteristic of this melt is represented by the reaction,
2AlCl4−↔Al2Cl7−+Cl−. (1)
In AlCl3-EMIM electrolyte, Al electrodeposition can only be successful in an acidic solution because the formation of the electroactive Al2Cl7− is formed only when the molar fraction of AlCl3 becomes larger than 0.5. In basic AlCl3-EMIM solutions, the only electroactive specie is AlCl4−, whose reduction potential is more negative than the breakdown potential of the organic cation from the electrolyte. The electrochemically active Al2Cl7− unsaturated ion reduces to Al at the cathode according to the following reaction,
4Al2Cl7−+3e−↔Al+7AlCl4−. (2)
For Al—Ni electrodeposition, AlCl3-EMIM-NiCl2 of desired molarity is required. Previous studies suggest that NiCl2 is difficult to dissolve in acidic AlCl3-BPC, while it is readily dissolved in basic melt. However, there have only been a few studies on the behavior of the dissolution of NiCl2 in AlCl3-EMIM and its electrochemical properties. Described below is the electrochemistry of Al—Ni deposition, the parameters that affect the alloy composition and microstructure, and synthesis and electrochemical properties of room-temperature electrolytes (molten salts) that can be used to produce electrodeposited Al—Ni alloys and Al/Ni multilayer structures. The electrolytes comprise an ionic solution including AlCl3, NiCl2, and an organic halide, such as AlCl3-EMIM-NiCl2.
Electrodeposition experiments were performed using a three-electrode setup inside an argon-filled glovebox (Mbraun Labstar, H2O and O2<1 ppm). A Gamry Reference 600 potentiostat was used for electrodeposition and cyclic voltammetry measurements. Acidic metal bases, including anhydrous aluminum chloride (AlCl3, 99.999%, Aldrich) and anhydrous nickel chloride (NiCl2, 99%, Alfa Aesar), were used as-received. 1-Ethyl-3-methylimidazolium chloride (EMIM, >98%, Lolitec) was heated at 60° C. for 3 days under vacuum to remove excess moisture. Al plate (99.99%, Alfa Aesar) and Al wire (99.99%, Alfa Aesar) were used as the counter and reference electrodes, respectively, unless specified otherwise. Three different materials: copper (Cu) plate (99.99%, Online Metals, 25×15×1 mm), Al plate (99.99%, Alfa Aesar, 25×15×1 mm), and tungsten (W) wire (99.99%, Sigma Aldrich, 1 mm diameter) were employed as the working electrodes. The exposed areas of the Al and Cu working electrodes were limited to 2.25 cm2 by covering the remainder of the areas with epoxy or electrochemical stop liquor. The Al electrodes were polished with 180-grit silicon carbide (SiC) paper and then dipped in an acid solution of 70% H3PO4, 25% H2SO4 and 5% HNO3 (by volume) for 10 minutes to remove the native oxides from the Al surface. The Cu electrodes were pretreated in an acid solution of 10% H2SO4 and 90% water (H2O) (by volume) for 30 seconds. The W electrode was used as received. The deposited structures were characterized using scanning electron microscopy (SEM) (Hitachi SU-70) and energy-dispersive X-ray spectroscopy (EDS) (EDAX-Phoenix). A cross-section of an Al/Ni bilayer was obtained by ion milling using focused ion beam microscopy (FIB) (FEI Quanta 200).
To study the dissolution behavior of NiCl2 in AlCl3-EMIM, 0.01 M NiCl2 was first directly added to a 2:1 molar ratio of AlCl3-EMIM electrolyte. After 24 hours of stirring, the clear electrolyte (
Further addition of AlCl3 was performed to shift the reduction potential of Al to support its deposition. It was noticed that AlCl3 was easily dissolved beyond 1:1 molar ratio of AlCl3:EMIM but could not reach 2:1 as excess AlCl3 precipitated without dissolution. This can be understood by the fact that Ni2+ ions consume some of the EMIM anions making less available reactive anions for Al3+ cations. Thus, the molarity ratio of the AlCl3:EMIM was limited to 1.5:1 for all experiments. The resultant electrolyte (hereafter referred as NiCl2-EMIM-AlCl3 electrolyte) was a clear brown solution and was used without further purification.
A voltage sweep starting from 2 V versus Al/Al3+ to −0.5 V and reversed back to 2 V was applied to determine the oxidation and reduction peaks suggesting dissolution and deposition of the respective metals or alloys, respectively. The peak shapes in the voltammograms depicted in
Cyclic voltammetry with similar parameters was conducted on the Cu electrode to study the variations in the peak potentials for Al and Ni deposition shown in
A number of samples with different parameters were deposited to study the effect of deposition potentials, duty ratios, and frequencies on alloy composition, as shown in
Samples 3 and 5 were deposited using the same potential, duty cycle ratio, and frequency in AlCl3-EMIM containing 0.026 M and 0.1 M of NiCl2, respectively. The Ni concentration increased nonlinearly from 2 to 6 at. % as the amount of NiCl2 increased due to the availability of more Ni and fewer Al ions shown by their peaks in the CV. This non-linear proportionality with a much greater deviation can also be observed when comparing samples 1 and 6.
Samples 5 and 6 with duty ratios 1:1 and 9:1, respectively, were deposited in AlCl3-EMIM containing 0.1 M NiCl2 using the same potentials. It was observed that the Al and Ni contents increased with increasing the time of the positive and negative cycles of the pulse, respectively. In Sample 5, the 9:1 ratio potential pulse spends most of the time in the negative cycle at −0.3 V responsible for depositing Al, while the positive pulse, which is just 1/10th of the total cycle, decreases the time for the deposition of Ni and stripping of Al. On the contrary, in Sample 6, the 1:1 ratio provides more time for Ni to be deposited. Also, since the reduction potential of Ni lies in close proximity of the oxidation potential of Al, Al stripping accompanies Ni deposition, resulting in lesser amount of Al in the mix.
The effect of frequency on the Al—Ni composition can be analyzed using Samples 3 and 4 deposited with frequencies 1 and 0.5 Hz with the same electrolyte, potential, and duty ratio. Decreasing the frequency by half resulted in almost twice the amount of Ni in the deposited alloy. With frequencies of 1 and 0.5 Hz, the deposition of Al and Ni takes place for 0.5 second and 1 second in each cycle, respectively. Since Ni deposition occurs via three-dimensional progressive nucleation, with more time for each cycle in the 0.5 Hz frequency, the current transient draws more current in 1 second as compared to that drawn in 2 cycles of 0.5 seconds in 1 Hz frequency. This increased current density on the Ni deposition cycle results in the increased Ni content.
Sample 7 was deposited on a smooth electrodeposited Cu substrate with the same potential, frequency, duty ratio, and electrolyte as Sample 5, which was deposited on a relatively rougher Cu substrate. Ni concentration was found to increase from 6 to 17.7 at. % using a smoother surface. The electrodeposited Cu substrate provides a much smoother surface with nano-scale roughness, which might favor metal nucleation resulting in better adherence of the Ni particles.
The SEM image of Sample 1 in
Application of this system to Al/Ni bilayers was also tested and revealed useful results. A successful bilayer sample with Ni deposited on electrodeposited Cu with a pulse potential of 0 and 0.78 V for 800 seconds, and Al deposited at a constant −0.3 V for 150 seconds in AlCl3-EMIM containing 0.026 M NiCl2 was prepared. The first cycle of the pulse potential waveform for the deposition of Ni was set to 0V. 0.78 V for the second cycle was chosen as the potential where the current becomes zero from voltammogram in
As described in the foregoing discussion, electrodeposition of Al—Ni alloys and Al/Ni multilayer structures have been successfully demonstrated. Dissolution of NiCl2 in an AlCl3-EMIM room-temperature melt was found to be favorable in basic electrolyte. A detailed study on the electrochemical properties of the electrolyte using cyclic voltammetry has been performed. The use of an electrochemically active Cu working electrode effects the electrochemistry of the electrolyte by dissolving Cu in the scan range of 1 to 2 V and introducing additional oxidation and reduction peaks pertaining to the stripping and deposition of Cu. The current density of Ni and Al oxidation and reduction peaks vary directly and indirectly to the amount of NiCl2 dissolved in the AlCl3-EMIM electrolyte respectively. The concentration of Ni in the Al—Ni alloys increased with the increase in amount of NiC2 dissolved in the melt, increase in the time period of positive potential cycle, decrease in frequency, and decrease in surface roughness of the working electrode. The Al—Ni alloys typically showed nodular morphology with a cauliflower structure. Flake structures, which were independent of surface roughness, were found to develop for a 1:1 duty ratio. XRD on the Al—Ni alloys suggests the presence of supersaturated FCC crystalline solid solution of Al and Ni. A uniform Al/Ni bilayer was successfully deposited in 1.5:1 AlCl3-EMIM containing 0.026 M NiCl2. Deposition of Al on Ni was achieved.
Referring next to block 12, AlCl3 is added to the NiCl2-organic halide mixture to obtain an AlCl3-organic halide-NiCl2 electrolyte solution. As described above, when the electrolyte solution contains small amounts of AlCl3, the electrolyte solution is basic. When the molar fraction of AlCl3 reaches 0.5 or greater, however, the electrolyte solution becomes acidic, which facilitates electrodeposition of Al. Accordingly, the AlCl3 is added in an amount sufficient to change the AlCl3-organic halide-NiCl2 electrolyte solution from a basic electrolyte solution to an acidic electrolyte solution. Accordingly, AlCl3 is added until the molar fraction of AlCl3 within the solution is 0.5 or greater. In some embodiments, AlCl3 is added to the electrolyte solution until a molar ratio of AlCl3:organic halide is 1.5:1. In some embodiments, the NiCl3 is added to the electrolyte solution until a molar ratio of NiCl3:AlCl3-organic halide is 0.024 to 0.1.
With reference next to block 14, working, reference, and counter electrodes can be provided (immersed) in the acidic AlCl3-organic halide-NiCl2 electrolyte solution and, with reference to block 16, a waveform is applied to the counter electrode using cyclic voltammetry to deposit Al and Ni on the working electrode. The various parameters of the cyclic voltammetry, such as the applied potential, the frequency, the duty cycle ratio, and time, can be selected depending upon the alloy or multi-layer structure that is desired. Notably, however, the electrolyte solution need not be heated and, therefore, electrodeposition can be performed at room temperature.
This application is the 35 U.S.C. § 371 national stage application of PCT Application No. PCT/US2016/044689, filed Jul. 29, 2016, where the PCT claims priority to U.S. Provisional Application Ser. No. 62/199,464, filed Jul. 31, 2015, both of which are herein incorporated by reference in their entireties.
Filing Document | Filing Date | Country | Kind |
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PCT/US2016/044689 | 7/29/2016 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
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WO2017/023743 | 2/9/2017 | WO | A |
Number | Name | Date | Kind |
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5552241 | Mamantov | Sep 1996 | A |
20060272949 | Detor et al. | Dec 2006 | A1 |
20110083967 | Ruan | Apr 2011 | A1 |
20110180413 | Whitaker | Jul 2011 | A1 |
20120118745 | Bao | May 2012 | A1 |
20130168258 | Nakano | Jul 2013 | A1 |
20140374263 | Cai et al. | Dec 2014 | A1 |
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62199464 | Jul 2015 | US |