Reversible aqueous aluminum metal batteries enabled by a water-in-salt electrolyte

Aluminum(Al),the most abundant metallic element on the earth crust,has been reckoned as a promising battery material for its the highest theoretical volume capacity(8046 mAh cm^(-3)).Being rechargeable in ionic liquid electrolytes,however,the Al anode and battery case suffer from corrosion.On the other hand,Al is irreversible in aqueous electrolyte with severe hydrogen evolution reaction.Here,we demonstrate a water-in-salt aluminum ion electrolyte(WISE)based on Al and lithium salts to tackle the above challenges.In the WISE system,water molecules can be confined within the Li^(+)solvation structures.This diminished Al^(3+)-H_(2)O interaction essentially eliminates the hydrolysis effect,effectively protecting Al anode from corrosion.Therefore,long-term Al plating/stripping can be realized.Furthermore,two types of high-performance full batteries have been demonstrated using copper hexacyanoferrate(CuHCF,a Prussian Blue Analogues)and LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM)as cathodes.The reversibility of Al anode laid the foundation for low cost rechargeable batteries suffering for large-scale energy storage.Broader context:Al batteries are expected to become a safe and sustainable alternative to lithium batteries.For decades,chase for a feasible Al secondary battery has not been successful.The key challenge is to find suitable cathode and electrolyte materials,together with which Al anode battery can function reversibly.Currently,fatal drawbacks have impeded the practical application of Al metal batteries(AMBs),such as sustained corrosion of Al anode and battery case in ionic liquid electrolytes,irreversibility issues as well as severe hydrogen evolution reaction during cycling in aqueous electrolyte.Therefore,electrolyte and their electrochemical kinetics play a vital role in the performance and environmental operating limitations of high-energy Al metal batteries.In this work,we demonstrate a nearly neutral Al ion water-in-salt electrolyte(WISE)to tackle the above challenges.The WISE shows excellent stability in the open atmosphere.The distinct solvation-sheath structure of Al^(3+)in the WISE system would protect Al metal anodes from corrosion and eliminate hydrogen evolution reaction effectively,further promoting the reversibility of Al metal anodes with dendrite-free morphology.Moreover,such a WISE exhibits superior compatibility with LiNi_(0.3)Co_(0.3)Mn_(0.3)O_(2)(NCM)and copper hexacyanoferrate(CuHCF)cathodes and long-term stabilities with high coulombic efficiency(CE)can be attained for full batteries with the WISE.The approach in this study can furnish an opportunity to develop reversible AMBs and lay the foundation for other potential multivalent-metalbased secondary batteries suffering from interface passivation and poor reversibility,which suggest the promise of multivalent metal batteries and their applications in large-scale energy storage.

Quick selection of aluminum galvanic anodes in oil brine via galvanic current

According to dynamics of coupled galvanic anode with carbon steel,the integral of galvanic current vs.time is approximately equal to actual current capacity of galvanic anode.Galvanic current of cast aluminum galvanic anode coupled with carbon steel is tested in3.5%NaCl solution and ambient temperature.Rapid evaluation the performance of galvanic anode using galvanic current is feasible,and the test time is20min.The galvanic current is used to select aluminum galvanic anodes in oil brine,and then test the galvanic anodes with impressed current test method.The result shows,the performance of galvanic anodes degrads in oil brine,but has not much difference in the two media to the preferable anodes,and the optimal galvanic anode is gained.

Effect of Deposition Temperature on Optical Properties of Porous Amorphous SiC Film

To study the effect of different deposition temperatures on the optical properties of porous SiC films,single crystal Si was used as the substrate,a layer of anodic aluminum oxide(AAO)film was transferred on the Si substrate by chemical method,and then a layer of SiC was deposited on anodic aluminum oxide(AAO)template to prepare porous fluorescent SiC film by magnetron sputtering.The deposition temperature was ranged from 373 to 873 K.The thickness of the porous SiC film coated on the AAO surface was around 283 nm.It is found that the porous SiC with the deposition temperature of 873 K has the strongest photoluminescence(PL)intensity excited by 375 nm laser.The time-resolved PL spectra prove that the PL is mainly from intrinsic light emitting of SiC.With the optimized process,porous amorphous SiC film may have potential applications in the field of warm white LEDs.

A comprehensive review on recent progress in aluminum-air batteries

The aluminum-air battery is considered to be an attractive candidate as a power source for electric vehicles(EVs) because of its high theoretical energy density(8100 Wh kg^(-1)), which is significantly greater than that of the state-of-the-art lithium-ion batteries(LIBs). However,some technical and scientific problems preventing the large-scale development of Al-air batteries have not yet to be resolved. In this review, we present the fundamentals, challenges and the recent advances in Al-air battery technology from aluminum anode, air cathode and electrocatalysts to electrolytes and inhibitors. Firstly, the alloying of aluminum with transition metal elements is reviewed and shown to reduce the selfcorrosion of Al and improve battery performance. Additionally for the cathode, extensive studies of electrocatalytic materials for oxygen reduction/evolution including Pt and Pt alloys, nonprecious metal catalysts, and carbonaceous materials at the air cathode are highlighted.Moreover, for the electrolyte, the application of aqueous and nonaqueous electrolytes in Al-air batteries are discussed. Meanwhile, the addition of inhibitors to the electrolyte to enhance electrochemical performance is also explored. Finally, the challenges and future research directions are proposed for the further development of Al-air batteries.

An interface-reconstruction effect for rechargeable aluminum battery in ionic liquid electrolyte to enhance cycling performances

Aluminum(Al) metal has been regarded as a promising anode for rechargeable batteries because of its natural abundance and high theoretical specific capacity. However, rechargeable aluminum batteries(RABs) using A1 metal as anode display poor cycling performances owing to interface problems between anode and electrolyte. The solid-electrolyte interphase(SEI) layer on the anode has been confirmed to be essential for improving cycling performances of rechargeable batteries. Therefore, we immerse the Al metal in ionic liquid electrolyte for some time before it is used as anode to remove the passive film and expose fresh Al to the electrolyte. Then the reactions of exposed Al, acid, oxygen and water in electrolyte are occurred to form an SEI layer in the cycle. Al/electrolyte/V_2 O_5 full batteries with the thin, uniform and stable SEI layer on Al metal anode perform high discharge capacity and coulombic efficiency(CE). This work illustrates that an SEI layer is formed on Al metal anode in the cycle using a simple and effective pretreatment process and results in superior cycling performances for RABs.

Evaluation of nanometer-sized zirconium oxide incorporated Al-Mg-Ga-Sn alloy as anode for alkaline aluminum batteries

Zirconium oxide nanoparticles with 0.4 wt.%and 0.8 wt.%are incorporated into the Al-0.65 Mg-0.05 Ga-0.15 Sn(wt.%)alloy anode(base alloy)in order to improve the performance of the resulting anodes.Electrochemical characterization of the reinforced alloys was done by potentiodynamic polarization,electrochemical impedance spectroscopy and galvanostatic discharge and corrosion behavior was evaluated using self-corrosion rate and hydrogen evolution in 4 mol/L KOH solution.The surface morphology of the alloys was also studied using field emission scanning electron microscope(FESEM).The obtained results indicate that the base alloy shows high corrosion rate in 4 mol/L KOH solution by releasing 0.47 m L/(min·cm^2)hydrogen gas,whereas the alloy containing 0.8 wt.%Zr O2 provides the lowest hydrogen evolution rate by releasing 0.32 m L/(min·cm^2)hydrogen gas.Furthermore,by increasing zirconium oxide nanoparticles,the corrosion current density of the aluminum anodes is decreased and their corrosion resistance increases significantly compared to the base alloy in alkaline solution.In addition,nanometer-sized zirconium oxide incorporated anodes exhibit the improved galvanic discharge efficiencies,so that 0.8 wt.%nano-zirconium oxide incorporated base alloy displays the highest power density and anodic utilization compared with the others in 4 mol/L KOH solution.

Preparation and Characterization of Fe Nanowire Arrays Embedded in Porous Anodic Aluminum Oxide Templates

Fe nanowire arrays are prepared by electrodeposition in porous anodic aluminum oxide template from a composite electrolyte solution. These nanowires have an uniform diameter of approximate 25 nm and a length in excess of 2.5 μm. The micrographs and crystal structures of Fe nanowires are studied by transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and X-ray diffraction(XRD). It is found that each nanowire is essentially a single crystal and has a different orientation in each array. Hysteresis loops of Fe nanowire array show that its easy magnetization direction is perpendicular to the sample plane.

Electrical Conductivity and Corrosion Resistanceof ZnFe _(2)O _(4) Based Materials Used as Inert Anodefor Aluminum Electrolysis

ZnFe 2O 4 and ZnFe 2O 4 based materials were tested to obtain the electrical conductivity and corrosion resistance in melting bath for aluminum electrolysis. The results proved that adequate additives, such as Ni 2O 3 CuO, Cu, ZnO and CeO 2 would increase the electrical conductivity, and the ZnFe 2O 4 based anodes with these additives were of good corrosion resistance. The current density on anode, the mole ratio of NaF/AlF 3 (MR) and the content of alumina in the bath effect the anode corrosion rate in different way.

Study on the Rare Earth Sealing Procedure of the Porous Film of Anodized 2024 Aluminum Alloy

The rare earth sealing procedure of the porous film of anodized aluminum alloy 2024 was studied with the fieldemission scanning electron microscope (SEM) and X-ray energy dispersive spectroscopy (EDS). The results show thatRE solution can form cerium oxide/hydroxides precipitation in the pores of the anodized coating at the beginning ofsealing. At the same time, the spherical deposits formed on the surface of the anodized coating created a barrierto the precipitation of RE solution in the pores. When the pore-structured anodizing film is covered all with thespherical deposits, RE conversion coating will form on the surface of the anodized coating. The reaction of thecoating formation was investigated by employing cyclic voltammetry. The results indicate that accelerator H2O2 actsas the source of O2 by carrying chemical reaction in course of coating formation. In the mean time, it maybe carrieselectrochemical reaction to generate alkaline condition to accelerate the coating formation. The porous structure ofthe film is beneficial to the precipitation of the cerium hydroxides film.

Influence of the operating parameters over the current efficiency and corrosion rate in the Hall–Heroult aluminum cell with tin oxide anode substrate material

A systematic laboratory study was conducted on current efficiency and corrosion obtained in cryolite-alumina melts with SnO2-Sb203-CuO ceramic inert anodes. The current efficiency （CE） was determined by measuring the total amount of oxygen evolved at the anode and was found to be ~ 95%. The influence of operating parameters （inter-elec- trode distance, temperature and current density） was evaluated. The quantitative interdependencies as well as the ranges of CE optima[ values were established （2-3 cm, 940-960 ℃ and 0.7-0.8 A.cm 2）. The corrosion process of these anodes was evaluated by the mass loss method. The evaluation also took care of the corrosion data, as the prob- lem of the anode corrosion appeared to be the main obstacle for the use of those anodes in the commercial cells.Low-ering of the ACD up to 2 cm did not aggravate anode corrosion.

CFD simulation of effect of anode configuration on gas–liquid flow and alumina transport process in an aluminum reduction cell

Numerical simulations of gas–liquid two-phase flow and alumina transport process in an aluminum reduction cell were conducted to investigate the effects of anode configurations on the bath flow, gas volume fraction and alumina content distributions. An Euler–Euler two-fluid model was employed coupled with a species transport equation for alumina content. Three different anode configurations such as anode without a slot, anode with a longitudinal slot and anode with a transversal slot were studied in the simulation. The simulation results clearly show that the slots can reduce the bath velocity and promote the releasing of the anode gas, but can not contribute to the uniformity of the alumina content. Comparisons of the effects between the longitudinal and transversal slots indicate that the longitudinal slot is better in terms of gas–liquid flow but is disadvantageous for alumina mixing and transport process due to a decrease of anode gas under the anode bottom surface. It is demonstrated from the simulations that the mixing and transfer characteristics of alumina are controlled to great extent by the anode gas forces while the electromagnetic forces(EMFs) play the second role.

Antibacterial Surface Treatment of Aluminum Materials

Aluminum specimens were anodized in a sulfuric acid bath, thensilver was electrodeposited in pores of the anodized aluminum byusing alternating current. The anodized aluminum with depositedsilver was tested for its antibacterial performance. The results showthat the antibacterial rates of the specimens are above 95/100against the growth of E. coli, P. Aeruginasa, S. faecalis and S.aureus. The morphology of the silver in pores of anodized aluminum ischaracterized by transmission electron microscopy, and themicrographs indicate that silver is assembled in the form ofnanowires with a diameter of 10 nm or 25 nm. The nanowires have astructure of parallel bright stripes alternating with parallel darkstripes.

FePt nano-stripes fabricated on anodic aluminum oxide templates

A new Fe Pt nanostructure with stripe-like patterns has been prepared by direct current（DC） magnetron sputtering on anodic aluminum oxide（AAO） templates. AAO templates anodized under low voltages（7 V） demonstrate self-organized,maze-like patterns, different from the conventional porous structures obtained at high voltages. Fe Pt thin films deposited on such templates tend to replicate the morphology of the templates. Although there is no obvious spatial ordering, the dimensions of the Fe Pt nano-stripes are highly uniform, due to the constrained growth along the transverse direction of the AAO pattern. The magnetic properties are strongly influenced by this unique morphology. While continuous films demonstrate strong exchange coupling, the dominant interaction in Fe Pt nano-stripes with the same nominal thickness is magnetostatic. The morphology also dictates the magnetization reversal behaviors, with thin films dominated by domain nucleation; while nano-stripes incline to reverse their magnetization by spin rotation. Our work demonstrates that selforganized AAO templates can be used to control the morphology and magnetic behavior of Fe Pt materials.

Fabrication of Aluminum/Single-Walled Carbon Nanotube Oxidation Films through CNT-Added Surface Treatment

CNT-added surface treatment (CAST) is a newly developed technology that incorporates single-walled carbon nanotubes (SWCNTs) into a metal surface through alternate current electrolysis using a dispersion of SWCNTs in an alkaline aqueous solution. We apply this method to Al-plates and characterize their surface morphology and components through scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. After CAST processing, protrusion structures of Al-oxide containing SWCNTs are formed on the surface of the Al-plate, and the surface morphology differs significantly from that of the surface of Al films treated through conventional anodic oxidation. The height and spacing of the protrusion structures formed on the surface of the CAST-treated Al-plates are 100 - 200 nm and 50 - 100 nm, respectively. In addition, we investigate the formation mechanism of the protrusion structure by applying a DC voltage between the working electrode (Al-plate) and a counter electrode immersed in a dispersion of SWCNTs in an alkaline aqueous solution. Comparing the Al-plate surface after treatment under both current directions, we propose a model for the formation process of protrusion structures containing SWCNTs based on catalyst surface etching.

Effects of gallium on electrochemical discharge behavior of Al-Mg-Sn-In alloy anode for air cell or water-activated cell

In order to evaluate the electrochemical properties of aluminum alloy anode under high current densities in alkaline electrolyte, the galvanostatic discharge, potentiodynamic polarization and hydrogen evolution tests of three experimental Al?Mg?Sn?In?(Ga) alloys were performed. The results show that the alloying element gallium improves the working potentials of experimental Al?Mg?Sn?In alloys under different discharge current densities. The average working potentials of the alloys containing gallium can reach?1.3 V under current density ranging from 650 to 900 mA/cm2, while those of alloy without Ga are only?1.0 V. Such phenomenon is attributed to the solid solution which can form amalgam with aluminum matrix. Such an amalgam can form the hydrolyzed species during the discharge process and lead to the corrosion infiltrating into aluminum matrix.

Electroless Deposition of Nickel Nanowire and Nanotube Arrays as Supports for Pt-Pd Catalyst for Ethanol Electrooxidation

Nickel nanowire and nanotube arrays as supports for Pt-Pd catalyst were prepared by elec- troless deposition with anodic aluminum oxide template. Pt-Pd composite catalyst was de- posited on the arrays by displacement reaction. SEM images show that the nickel nanowires have an average diameter of I00 nm and the nickel nanotubes have an average inner diameter of 200 nm. EDS scanning reveals that elemental Pt and Pd disperse uniformly on the arrays. Cyclic voltammetry study indicates that the nickel nanotube array loaded with Pt-Pd pos- sesses a higher electrochemical activity for ethanol oxidation than the nickel nanowire array with Pt-Pd.

Quantificational Etching of AAO Template

Ni nanowires were prepared by electrodeposition in porous anodized aluminum oxide （AAO） template from a composite electrolyte solution. Well-ordered Ni nanowire arrays with controllable length were then made by the partial removal of AAO using a mixture of phosphoric acid and chromic acid （6 wt pct H3PO4：1.8 wt pct H3CrO4）. The images of Ni nanowire arrays were studied by scanning electron microscopy （SEM） to determine the relationship between etching time and the length of Ni nanowire arrays. The results indicate that the length of nanowires exposed from the template can be accurately controlled by controlling etching time.

Interfacial phenomena in electric field-assisted anodic bonding of Kovar/Al film-glass

Anodic bonding of glass to Kovar alloy coated with Al film (Glass Al film/Kovar) was performed in the temperature range of 513 ～ 713?K under the static electric voltage of 500?V in order to investigate the interfacial phenomena of Al glass joint. The results reveal that Na and K ions within the glass are displaced by the applied field from the anode side surface of the glass to form depletion layers of them. The K ion depletion layer is narrow and followed by a K pile up layer, and both the two layers are formed within the Na depletion layer. The width of the Na and K depletion layers is increased with increasing bonding temperature and time. The activation energies for the growth of both depletion layers were close to that for Na diffusion in the glass. TEM observations reveal that Al film coated at the surface of Kovar alloy is oxidized to amorphous Al 2O 3 containing a few of Fe, Ni and Co by oxygen ions from the glass drifted by high electric field during bonding. The amount of Fe ions diffusing into the glass adjacent to the anode is significantly low due to the presence of Al film between Kovar alloy and the glass. As a result, the amorphous reaction layer of Fe Si O in the glass near the interface is avoided which is formed in Kovar glass joints.

Electrochemical Fabrication of Pd-Ag Alloy Nanowire Arrays in Anodic Alumina Oxide Template

The synthesis of Pd-Ag alloy nanowires in nanopores of porous anodic aluminum oxide （AAO） template by electrochemical deposition technique was reported. Pd-Ag alloy nanowires with 16%-25% Ag content are expected to serve as candidates of useful nanomaterials for the hydrogen sensors. Scanning electron microscopy （SEM） and energy dispersed X-ray spectroscopy （EDX） were employed to characterize the morphologies and compositions of the Pd-Ag nanowires. X-ray diffraction （XRD） was used to characterize the phase properties of the Pd-Ag nanowires. Pd-Ag alloy nanowire arrays with 17.28%-23.76% Ag content have been successfully fabricated by applying potentials ranging from -0.8 to -1.0 V （vs SCE）. The sizes of the alloy nanowires are in agreement with the diameter of AAO nanopores. The underpotential deposition of Ag＋ on Pd and Au plays an important role in producing an exceptionally high Ag content in the alloy. Alloy compositions can still be controlled by adjusting the ion concentration ratio of Pd^2＋ and Ag＋ and the electrodeposition processes. XRD shows that nanowires obtained are in the form of alloy of Pd and Ag.

Highly ordered TiO_2 nano-pore arrays fabricated from a novel polymethylmethacrylate/polydimethylsiloxane soft template

A novel soft polymer template containing a double-layer structure,which includes a thin layer of polymethylmethacrylate(PMMA)used as a pattern layer and a thicker layer of polydimethylsiloxane(PDMS)used as a back layer,was fabricated from a replica molding process.Anodic aluminum oxide(AAO)template was used as the replica mold to be replicated to the polymethylmethacrylate layer by a thermal infiltration process under a vacuum condition.Results indicate that PMMA/PDMS soft templates with different sizes could be easily fabricated from the as-prepared AAO replica mold.The PMMA/PDMS soft templates were then employed to imprint a TiO_2 gel for achieving TiO_2 nano-pore arrays.After the imprinting process,the PDMS layer was firstly peeled off and the PMMA layer was then removed into acetonitrile,which can avoid any demolding problems like damages or distortions.The TiO_2 nano-pore arrays with the crystalline of anatase could be obtained at a heat treatment temperature of 450°C.