Emerging rechargeable aqueous aluminum ion battery:Status,challenges,and outlooks

Aluminum ion battery(AIB)technology is an exciting alternative for post-lithium energy storage.AIBs based on ionic liquids have enabled advances in both cathode material development and fundamental understanding on mechanisms.Recently,unlocking chemistry in rechargeable aqueous aluminum ion battery(AAIB)provides impressive prospects in terms of kinetics,cost,safety considerations,and ease of operation.To review the progress on AAIB,we discuss the critical issues on aluminum electrochemistry in aqueous system,cathode material design to overcome the drawbacks by multivalent aluminum ions,and challenges on electrolyte design,aluminum stripping/plating,solid-electrolyte interface(SEI)formation,and design of cathode materials.This review aims to stimulate exploration of high-performance AAIB and rationalize feasibility grounded on underlying reaction mechanisms.

Chemical Species of Aluminum Ions in Acid Soils *1

Soil samples collected from several acid soils in Guangdong, Fujian, Zhejiang and Anhui provinces of the southern China were employed to characterize the chemical species of aluminum ions in the soils. The proportion of monomeric inorganic Al to total Al in soil solution was in the range of 19% to 70%, that of monomeric organic Al (Al OM) to total Al ranged from 7.7% to 69%, and that of the acid soluble Al to total Al was generally smaller and was lower than 20% in most of the acid soils studied. The Al OM concentration in soil solution was positively correlated with the content of dissolved organic carbon (DOC) and also affected by the concentration of Al 3+ . The complexes of aluminum with fluoride (Al F) were the predominant forms of inorganic Al, and the proportion of Al F complexes to total inorganic Al increased with pH. Under strongly acid condition, Al 3+ was also a major form of inorganic Al, and the proportion of Al 3+ to total inorganic Al decreased with increasing pH. The proportions of Al OH and Al SO 4 complexes to total inorganic Al were small and were not larger than 10% in the most acid soils. The concentration of inorganic Al in solution depended largely on pH and the concentration of total F in soil solution. The concentrations of Al OM, Al 3+ ,Al F and Al OH complexes in topsoil were higher than those in subsoil and decreased with the increase in soil depth. The chemical species of aluminum ions were influenced by pH. The concentrations of Al OM, Al 3+ , Al F complexes and Al OH complexes decreased with the increase in pH.

Influence of Aluminum Ions Implantation on Corrosion Behavior of Zircaloy-2 Alloy in 1 M H_2SO_4

The specimens were implanted with aluminum ions with fluence ranging from 1× 10^16 to 1× 10^17 ions/cm^2 to study the effect of aluminum ion implantation on the aqueous corrosion behavior of zircaloy-2 by metal vapor vacuum arc source （MEVVA） at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy （XPS） and Auger electron spectroscopy （AES）, respectively. Transmission electron microscopy （TEM） was used to examine the microstructure of the aluminum-implanted samples. Glancing angle X-ray diffraction （GAXRD） was employed to examine the phase transformation due to the aluminum ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircaloy-2 in a 1 M H2SO4 solution. It is found that a significant improvement was achieved in the aqueous corrosion resistance of zircaloy-2 implanted with aluminum ions. Finally, the mechanism of the corrosion behavior of aluminum- implanted zircaloy-2 was discussed.

Comments on “An ultrafast rechargeable aluminum ion battery”

Nature published an article'An ultrafast rechargeable aluminum ion battery'On April 6,2015.The authors used many new materials to compose the cell,such as three-dimensional graphitic-foam as the cathode,an ionic liquid electrolyte.The experimental cell has shown well-defined discharge voltage plateaus near 2 V.The cell is mechanically bendable and foldable without affecting its operation.

THERMODYNAMIC PROPERTIES OF AQUEOUS ALUMINUM ION, Al^(3+) (aq)^+

The heat effect of the reaction between metallic aluminum and HCl(aq) solution of various concentrations were calorimetrically determined. Combining with the thermodynamic properties of related substances led to the thermodynamic properties of Al3+ (aq)

Aluminum Ion Occupancy in the Structure of Synthetic Saponites

Saponite has been widely used in a number of industrial fields because of the higher surface acidity and thermal stability when compared with other clay minerals (Alexander and Dubois, 2000; Casagrande et al., 2005). Due to its limited natural resource, synthesis of saponite has attracted much attention during the last two decades (Vogels et al., 2005; Bisio et al., 2008). The main aim of this study is to investigate occupancy of Al ions and its effect on the structure of synthetic saponites.

Sensitivity of Barley Varieties to Aluminum Ions: Separately Effects and Combine with Iron Ions

Differences in the barley varieties have been revealed from tolerance to iron (Fe) and aluminum (Al) ions as well as to their combined effect. Received results allowed to separate barley variety into some (three) groups: the first—Al-tolerant varieties, the second—Al-sensitive ones and third—moderately resistant variety. The increased concentration of Fe had practically no effect on biometric (seed germination energy) and cytogenetics (frequency of chromosome aberrations and mitotic index) parameters as compared to the reference values. At the same time, iron ion significantly reduces the phytotoxic effect for Al-tolerant varieties in case of these elements jointly presented in solution.

Realizing the Long Lifespan of Molybdenum Trioxide in Aqueous Aluminum Ion Batteries Through Potential Regulation

MoO_(3) is one of the most promising anode materials for aqueous aluminum batteries due to its high theoretical capacity and suitable aluminum insertion/de-insertion potential.However,the inferior cycling stability limits its further application,and the failure mechanism is still unclear.In this article,we provide a straightforward potential regulation technique to manage phase evolution during the charge/discharge process,which ultimately results in a markedly enhanced MoO_(3) electrode cycling stability.The failure mechanism study reveals that the excessive oxidation of the electrode during charge/discharge generates the H_(0.34)MoO_(3) phase,which has high solubility and is the primary cause of MoO_(3) deactivation.Although the dissolved Mo species will be deposited onto the electrode sheet again,the deposition is not electrochemically active and cannot contribute to the capacitance.Controlling the cutoff potential prevented the production of H_(0.34)MoO_(3),resulting in excellent cycling performance(80.1% capacity retention after 4000 cycles).The as-assembled α-MoO_(3)//MnO_(2) full battery exhibits high discharge plateaus(1.4 and 0.9 V),large specific capacity(200 mAhg^(-1) at 2 Ag^(-1)),and ultra-high coulombic efficiency(99%).The research presented here may contribute to the development of highly stable electrode materials for aqueous batteries.

Reversible Al^(3+) storage mechanism in anatase TiO_(2) cathode material for ionic liquid electrolyte-based aluminum-ion batteries

Rechargeable aluminum ion battery(AIB) with high theoretical specific capacity, abundant elements and low cost engages considerable attention as a promising next generation energy storage and conversion system. Nevertheless, to date, one of the major barriers to pursuit better AIB is the limited applicable cathode materials with the ability to store aluminum highly reversibly. Herein, a highly reversible AIB is proposed using mesoporous TiO2 microparticles(M-TiO2) as the cathode material. The improved performance of Ti O2/Al battery is ascribed to the high ionic conductivity and material stability, which is caused by the stable architecture with a mesoporous microstructure and no random aggregation of secondary particles. In addition, we conducted detailed characterization to gain deeper understanding of the Al^(3+) storage mechanism in anatase Ti O2 for AIB. Our findings demonstrate clearly that Al^(3+)can be reversibly stored in anatase TiO2 by intercalation reactions based on ionic liquid electrolyte. Especially, DFT calculations were used to investigate the accurate insertion sites of aluminum ions in M-Ti O2 and the volume changes of M-TiO2 cells during discharging. As for the controversial side reactions in AIBs, in this work, by normalized calculation, we confirm that M-Ti O2 alone participate in the redox reaction. Moreover, cyclic voltammetry(CV) test was performed to investigate the pseudocapacitive behavior.

An amorphous carbon-graphite composite cathode for long cycle life rechargeable aluminum ion batteries

Natural graphite is investigated as the cathode for aluminum ion batteries in recent years. However, some drawbacks of the natural graphite such as severe volume swelling shorten its lifetime, In this work, we prepared a composite material by depositing an amorphous carbon on the graphite paper, The composite was used as a cathode to study the electrochemical performance in aluminum ion batteries. The charge/discharge results showed that the composite could exhibit a longer cycle life than the graphite paper, Electrochemical analyses demonstrated that the interface between the amorphous carbon and the graphite paper made a major contribution to the improvement of the cycling stability.

Non-stoichiometric CoS_(1.097) nanoparticles prepared from CoAl-layered double hydroxide and MOF template as cathode materials for aluminum-ion batteries

As a main force in the energy evolution,lithium-ion batteries(LIBs)have been extensively studied in recent decades and are widely used in energy storage and portable electronic products as a result of their advantages of high working voltage and long cycle performance.

Development of a new method for analyzing free aluminum ions(Al^(3+)) in seafood using HPLC-ICP-MS

This paper presents a novel method for simultaneous online examination of free aluminum ions(Al3+)in seafood,using solidphase extraction and high-performance liquid chromatography online with inductively coupled plasma mass spectrometry(SPEHPLC-ICP-MS),without post-column reaction.The optimum conditions for chromatographic separation of Al3+were achieved using an IonPac CS5A analytical column with an IonPac CG5A guard column.The mobile phase consisted of 0.040 mol/L LiOH,0.0060 mol/L 2,6-pyridinedicarboxylic acid,and 0.090 mol/L CH3COOH(pH 4.7).The free Al3+ions in seafood were extracted by shaking with the mobile phase at 70°C for 2 h.SPE was conducted using an Oasis MCX,3cc/60 mg,30μm column,which was activated and equilibrated with 2 mL of methanol and 4 mL of deionized water before use.HCl(0.075 mol/L,2 mL)was used to wash inorganic Al from the SPE column.The standard recoveries of Al3+were all above 89%and the relative standard deviations were all below 5%.The proposed method was successfully used for the examination of Al3+in seafood samples,and the results were similar to those obtained using the static equilibrium method.

Role of Chloride Ion and Dissolved Oxygen in Electrochemical Corrosion of AA5083-H321 Aluminum-Magnesium Alloy in NaCl Solutions under Flow Conditions

Flow-induced corrosion consists electrochemical and mechanical components. The present paper has to assessed the role of chloride ion and dissolved oxygen in the electrochemical component of flow induced corrosion for AA5083-H321 aluminum-magnesium alloy which is extensively used in the construction of high-speed boats, submarines, hovercrafts, and desalination systems, in NaCI solutions. Electrochemical tests were carried out at flow velocities of 0, ：2, 5, 7 and 10 m/s, in aerated and deaerated NaCI solutions with different sodium chloride concentrations. The results showed that the high rate of oxygen reduction under hydrodynamic conditions causes an increase in the density of pits on the surface. The increase of chloride ions concentration under flow conditions accelerates the rate of anodic reactions, but have no influence on the cathodic reactions. Thus, in the current work, it was found that under flow conditions, due to the elimination of corrosion products inside the pits, corrosion resistance of the alloy is increased.

Effects of cupric ions on the corrosion behavior of aluminum alloy 5A02 in ethylene glycol–water solution

The effects of cupric ions on the corrosion behavior of aluminum alloy 5A02 in ethylene glycol–water solutions were studied by potentiodynamic polarization,electrochemical noise(EN),and complementary techniques including scanning electron microscopy(SEM),atomic force microscopy(AFM),and X-ray photoelectron spectroscopy(XPS). A positive corrosion potential and increased corrosion current were observed due to the deposition of copper. The results demonstrate that the main corrosion type was pitting and the increasing cupric ion concentration augmented the pitting density. The pits became larger and deeper as a result of the embedment of copper into the surface of the alloy. Cupric ions were preferentially deposited at the defects around the secondary phase,leading to the formation of Al–Cu microgalvanic couples,which increased the corrosion rate. The corrosion rate gradually reached a stable value as the concentration of cupric ions was increased beyond 10 mmol/L.

Structure and tribological properties of modified layer on 2024 aluminum alloy by plasma-based ion implantation with nitrogen/titanium/carbon

aluminum alloy was implanted with nitrogen then titanium finally carbon by plasma-based ion implantatio to form a gradient layer. The structure and tribological properties of the layer were investigated. Its composition profiles and chemical states were analyzed with X-ray photoelectron spectroscopy(XPS). The surface carbon layer was analyzed by Raman spectrum. The appearances were observed by atomic force microscope (AFM). The surface hardness was measured with the mechanical property microprobe. The dry wear tests against GCr15 steel ball at various sliding loads were performed with a ball-on-disk wear tester in ambient environment. The results show that the thickness of the modified layer is 1 200 nm, the carbon layer is a smooth and compact diamond-like carbon(DLC) films, and the carbon-titanium interface is broadened due to carbon ions implantation, resulting in a good composition and structure transition between DLC films and titanium layer. Surface hardness is improved markedly, with a slow and uniform change. Tribological properties are improved greatly although they reduce with the increase of sliding loads because the modified layer becomes thin rapidly.

XPS INVESTIGATION OF NITROGEN IONS IMPLANTED INTO ALUMINUM ALLOY BY PLASMA BASED ION IMPLANTATION

Aluminum alloy 2024 has been implanted with nitrogen ions at various doses by plasma based ion implantation. The introduction of energetic ions causes structural change within the near surface region of the solid. The samples have been characterized by X-ray Photoelectron Spectroscopy at various depths. The chemical states of Al and N were identified by deconvolution of the recorded XPS spectra. After plasma based ion implanted nitrogen into aluminum, not only the AlN precipitates but also super saturated solution of nitrogen forms. The presence of aluminum in different chemical states is corresponding to Al, AlN and Al2O3. The majority of nitrogen is in the form of the supersaturated solution. With the increase of nitrogen dose, the amount of AlN precipitates increases.

Ultra-High Mass-Loading Cathode for Aqueous Zinc-Ion Battery Based on Graphene-Wrapped Aluminum Vanadate Nanobelts

Rechargeable aqueous zinc-ion batteries(AZIBs)have their unique advantages of cost efficiency,high safety,and environmental friendliness.However,challenges facing the cathode materials include whether they can remain chemically stable in aqueous electrolyte and provide a robust structure for the storage of Zn2+.Here,we report on H11Al2V6O23.2@graphene(HAVO@G)with exceptionally large layer spacing of(001)plane(13.36?).The graphene-wrapped structure can keep the structure stable during discharge/charge process,thereby promoting the inhibition of the dissolution of elements in the aqueous electrolyte.While used as cathode for AZIBs,HAVO@G electrode delivers ideal rate performance(reversible capacity of 305.4,276.6,230.0,201.7,180.6 mAh g?1 at current densities between 1 and 10 A g?1).Remarkably,the electrode exhibits excellent and stable cycling stability even at a high loading mass of^15.7 mg cm?2,with an ideal reversible capacity of 131.7 mAh g?1 after 400 cycles at 2 A g?1.

Effect of target temperature on microstructure of aluminum surface layer modified by plasma based ion implantation

Aluminum (99.6% purity) was implanted with nitrogen ions to a total dose of 6×10 17 cm -2 at different temperatures (from 50 ℃ to 400 ℃) by plasma based ion implantation (PBII). The surface microstructure was investigated by glancing angle X ray diffraction (GXRD), X ray photoelectron spectroscopy (XPS) and cross sectional transmission electron microscopy (XTEM). The results of GXRD and XTEM showed that there was an amorphous layer on the outer surface, and fine dispersion of AlN precipitates was found under the amorphous layer. The size of AlN precipitates strongly depended on the target temperature, with the increase of the target temperature, the size of AlN precipitates became larger. The excess nitrogen atoms can diffuse or migrate to the lower nitrogen concentration regions by radiation enhanced diffusion. The results of XPS further indicated that it was easier to form AlN precipitates at a higher target temperature, and the depth profile of nitrogen broadened.

Deposition of chromium aluminum nitride coatings by arc ion plating

Cr-Al-N ternary coatings were deposited by arc ion plating method using isolated Cr target and Al target. The influence of AlN content on the phase change was studied by synthesizing Cr1-xAlxN coatings with different x values. The effects of substrate negative bias on the surface morphology,deposition rate and phase structure were investigated. As the aluminum content increases,the structure of(Cr1-xAlx)N changes from B1(NaCl) phase to B4(wurtzite) phase. The critical content of AlN solubilized in B1(NaCl) lattice is close to 0.7. With the increasing pulse negative bias,the deposition rate decreases constantly,the droplet contamination is more serious,the ion-etching effect on coating surface is more obvious,and the change of preferred orientation and the shift of XRD peak take place.

Tribological properties of 2024 aluminum alloy plasma-based ion implanted with nitrogen then titanium

aluminum alloy was implanted with nitrogen then titanium at different titanium target sputtering currents by plasma-based ion implantation(PBII). The appearances were observed by atomic force microscope, and the surface hardness was measured with Knoop hardness tester and the mechanical property microprobe. Ball-on-disc dry wear experiments were performed under ambient air conditions, to study the tribological properties of the modified layers against GCr15 steel ball, employing various loads and a constant sliding speed. After dual modifications, surface hardness at 100 nm depth could reach to 9 GPa, increasing by about 5 times; tribological properties at lower load(e.g. 1 N) were obviously improved, with the friction coefficient(below 0.2) decreasing by over 60%, and the wear life(800 times) increasing by about 5 times. Meanwhile, with the increase of the sputtering current, the appearance is smooth, the surface hardness tends to a slow and even variation, the wear life presents a parabola-like change, and the friction coefficient and the adhesive wear degree decrease. However, tribological properties are reduced with the increase of the load due to the modified layer rapidly getting thin.