Mid Sweden University

The 99.99% Al used for negative Al electrodes in aluminum-based battery studies is expensive. This is primarily due to the complex challenges associated with fabricating 99.99% Al, particularly the removal of Fe impurities from Al melts. Despite the importance of this issue for the future commercialization of Al-based batteries, it has been largely overlooked. This work accordingly studied the plating/stripping behavior of Al containing 1 wt % iron (Al 1% Fe) as an alternative electrode using conventional ([EMIm]Cl and AlCl3) electrolyte. Simultaneously, the impact of the surface microstructure of Al 1% Fe on the plating/stripping behavior was examined. The results indicate that the difference in the plating/stripping cycling of Al 1% Fe alloys and 99.99% Al is negligible. Thus, Al 1% Fe negative electrodes could serve as an efficient and commercially viable alternative to 99.99% Al for plating/stripping in Al-based batteries. This is an essential finding because facile and commercial fabrication of Al 1% Fe electrodes is absolutely feasible. The results are further discussed in terms of the impact of the Al surface microstructure (i.e., grain size, defect density, grain boundary distribution, crystal orientation, and intermetallic phases) on plating/stripping behavior. Moreover, this study provides insights into how the interphase layer formed on Al electrodes influences plating/stripping behavior. 

Considerable research has been devoted to the development of cathode materials for Al-ion batteries, but challenges remain regarding the behavior of aluminum anodes. Inert oxide (Al2O3) film on Al surfaces presents a barrier to electrochemical activity. The structure of the oxide film needs to be weakened to facilitate ion transfer during electrochemical activity. This study addresses oxide film challenges by studying Al alloy anodes with different iron content. The results reveal that using an anode of 99% Al 1% Fe in a cell increases the cycling lifetime by 48%, compared to a 99.99% Al anode. The improvement observed with the 99% Al 1% Fe anode is attributed to its fractional surface area corrosion being about 12% larger than that of a 99.99% Al anode. This is coupled to precipitation of a higher number of Al3Fe particles, which are evenly scattered in the Al matrix of 99% Al 1% Fe. These Al3Fe particles constitute weak spots in the oxide film for the electrolyte to attack, and access to fresh Al. The addition of iron to an Al anode thus offers a cheap and easy route for targeting the oxide passivating film challenge in Al-ion batteries.

Recently, much research has investigated nanocomposites and their properties for the development of energy storage systems. Supercapacitor performance is usually enhanced by the use of porous electrode structures, which produce a larger surface area for reaction. In this work, a biocompatible polymer of starch medium was used to create the porous nanostructure. Two powders, i.e., Nickel molybdate/reduced graphene oxide (NiMoO4-rGO) and Nickel molybdate/nitrogen-doped reduced graphene oxide (NiMoO4-NrGO), were synthesized using the deposition method in a medium containing starch, nickel nitrate salts, sodium molybdate, and graphene oxide powder. In terms of electrochemical performance, the NiMoO4-NrGO electrode displayed a higher specific capacitance, i.e., 932 Fg−1 (466 Cg−1), than the NiMoO4-rGO electrode, i.e., 884 Fg−1 (442 Cg−1), at a current density of 1 Ag−1. In fact, graphene oxide sheets could lose more oxygen groups in the presence of ammonia, resulting in increased electrical conductivity. For the asymmetric supercapacitor of NiMoO4-NrGO//AC, the specific capacitance at 1 Ag−1, energy density, and power density were 101.2 Fg−1 (111.32 Cg−1), 17 Wh kg−1, and 174.4 kW kg−1, respectively. In addition, this supercapacitor material displayed a good cycling stability of over 82%.

Although ionic liquid electrolytes (ILs) are environmentally unfriendly, they are the most common electrolyte used in aluminum-ion batteries (AIB). Aqueous electrolytes offer a more sustainable alternative, but problem with oxide passivating barrier on Al surface becomes more profound. Recently, a new sub-class of aqueous electrolytes, water-in-salt (WIS) of (AlCl3·6H2O), has been considered, but experimental validation of the behavior of the Al electrode over cycling is required. This work investigates aluminum/graphitic cells using WIS electrolytes with a mass ratio of salt to water of 4, 8, and 12 and finds that they show similar trends in cycling performance. The degradation observed over cycling has been attributed to the formation of a detrimental solid electrolyte interphase (SEI) layer on the Al surface. It was found that WIS 4 increased Al corrosion, resulting in a slightly higher capacity and longer cycling life. Metallurgical observation showed that the Al matrix has a tendency to initiate corrosion around Al3Fe intermetallic phases in both WIS and ILs. This implies that the presence of Al3Fe particles allows the electrolyte to break the oxide barrier and access the bulk Al. These results suggests that metallurgical treatments are important to enhance the electrochemical performance of AIB.

Chemical composition analysis using sampling practices in as-cast aluminum alloys are not accurate enough. Optical emission spectrometry (OES) analyses of samples taken at specified milling depths do not match the desired nominal composition due to segregation phenomenon. Moreover, macrosegregation profiles within samples cast with current molds often exhibit significant variations. Various types of molds have been tested in the past to solve this problem, but none have had a satisfactory outcome. This paper presents research on a novel mold with an insulated periphery designed to yield more accurate sampling tests. The results from samples made with the insulated periphery mold show segregation profiles with good reproducibility. A value close to the nominal composition was observed at 6–7 mm milling depth. The reproducibility of segregation profiles is correlated to one-dimensional solidification, minimizing surface segregation areas, and melt convection.

The cycling performance of supercapacitors sometimes becomes limited when electrode materials slough off during frequent charge-discharge cycles, due to weak bonding between the active material and the current collector. In this work, a flexible graphite foil substrate was successfully used as the current collector for supercapacitor electrodes. Graphite foil substrates were treated in different ways with different acid concentrations and temperatures before being coated with an active material (NiMoO4/nanographite). The electrode treated with HNO3 (65%) and H2SO4 (95%) in a 1:1 ratio at 24 degrees C gave better electrochemical performance than did electrodes treated in other ways. This electrode had capacitances of 441 and 184 Fg(-1) at current densities of 0.5 and 10 Ag-1, respectively, with a good rate capability over the current densities of the other treated electrodes. SEM observation of the electrodes revealed that NiMoO4 with a morphology of nanorods 100-120 nm long was properly accommodated on the graphite surface during the charge-discharge process. It also showed that treatment with high-concentration acid created an appropriately porous and rough surface on the graphite, enhancing the adhesion of NiMoO4/nanographite and boosting the electrochemical performance.

Severe hot tearing has been observed during DC casting of modified AA3000 alloys with additions of Cu, Ti, and Zr, although these alloys are regarded as rather easy to cast. Extensive studies have been performed on both synthetic and industrial AA2000, AA6000, and AA7000 alloys, but less data are available for AA3000 alloys. This work was thus initiated to investigate the hot tearing susceptibility of AA3000 alloys with varying alloy element content using constrained rod casting molds. The results showed that the Cu and Fe content have a major impact on hot tearing resistance, while the effects of Zr and Ti are minor. Cu in a range from 0.3 to 1.2 wt pct significantly increased the hot tearing tendency. This is due to the existence of high eutectic fractions at low temperatures, as well as porosity formation associated with bad feeding at the end of solidification. A strong cracking tendency was observed below an Fe content 0.2 wt pct owing to decreased precipitation of the Al6(Mn, Fe) phase. It was found that primary Al6(Mn, Fe) phases lead to early bridging between the grains, which reinforces the alloy during the vulnerable temperature range for hot tearing. Zr and Ti additions weakly enhanced or reduced hot tearing severity, respectively.

The dissolution of Mn and Fe in liquid Al presents a challenge due to their high melting points and low diffusivity. A literature review reveals that the existing knowledge of the processes involved in the dissolution of both Fe and Mn in liquid Al is rather ambiguous. Thus, this work aimed to obtain more detailed insights into the dissolution behavior of Mn and Fe in various Al melts. The results of the Mn dissolution tests showed that three intermediate phases were involved in the dissolution process, all of which exhibited a smooth interface between Mn and the liquid. These three phases were identified as the γ2, Al11Mn4, and µ phases which grow slowly, penetrating the Mn particles. The results of the Fe dissolution tests showed that in pure Al, the Al5Fe2 phase dominates the dissolution process and penetrates the Fe particles. The addition of Ti into the molten Al alters the intermetallic compound formation by replacing Al5Fe2 by Al2Fe. The addition of Si significantly inhibited the Fe dissolution kinetics. A theoretical approach based on Ficks’ law was used to explain the experimentally obtained Mn and Fe dissolution rates. It showed that the surface area and shape of the additives significantly affected the dissolution processes.

The quality of DC cast Al alloys is highly dependent on melt batch composition and impurity level in the molten alloy. The chemical composition and cleanliness of a melt is controlled through the melt treatment operations, carried out while the melt is still in the furnace before casting starts. The present work has studied some of these operations and associated problems such as slow dissolution of alloying elements, non-reproducibility in chemical composition analysis and inclusions.

 The results of the dissolution of the alloy elements Mn and Fe showed different behaviors.  For Mn three intermediate phases were involved, all of which exhibited a smooth interface between Mn and the liquid. These three phases were identified as the γ₂, Al₁₁Mn₄, and µ phases, which grow slowly towards the dissolving Mn particles. The results from the Fe dissolution revealed that only one phase dominates the process, Al₅Fe₂, which penetrates the Fe particles with an irregular interface.

The interaction between Mn and Ti additions to AA3003 alloys and consequences for the solidification and precipitation behavior was investigated. The study could map the limits for formation of an earlier unknown AlMnTi phase, which formed large particles, detrimental for subsequent rolling operations.

Different sampling procedures for chemical composition analysis were studied, and a novel approach was proposed. A mould with an insulated periphery provided one-dimensional solidification, which gave compositions close to nominal.

 Inclusion distributions along as-cast billets were studied as a function of different holding times, and thus different grades of sedimentation. Holding times longer than 30 minutes did not show any improvements.  It was also shown that if melt remaining in the furnace at end of casting is less than about 3000 kg, the sedimented inclusions are stirred into the bulk again, and can enter into the end of the billet.

The impact on hot tearing susceptibility of different Cu and Fe contents for AA3000 alloys was studied. Cu contents in a range from 0.3 to 1.2 wt%  significantly increase the hot tearing tendency, which was attributed to bad feeding at end of solidification. Decreasing of the Fe content below 0.2 wt%, gives a strong cracking tendency, owing to decreased precipitations of the Al₆(Mn,Fe) phase, which contributes to early bridging and thus reinforcement between grains.