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.

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.

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.

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.

Theoretical calculations of hyperfine splitting,Zeeman shifts,and isotope shifts of^(27)Al^(+)and logical ions in Al^(+)clocks

Based on the multiconfiguration Dirac-Hartree-Fock(MCDHF)method,similar models are employed to simultaneously calculate the first-order and second-order Zeeman coefficients as well as the hyperfine interaction constants of the related energy levels of ^(27)Al^(+)and its logical ions ^(9)Be^(+)and^(25)Mg^(+)in the^(27)Al^(+)optical clock.With less than 0.34%deviations from experimental values in Zeeman coefficients of^(27)Al^(+),these calculated parameters will be of great help for better evaluation of the systematic uncertainty.We also calculate the isotope shift parameters of the related energy levels,which could extend our knowledge and understanding of nuclear properties of these ions.

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.

Graphite recycling from spent lithium-ion batteries for fabrication of high-performance aluminum-ion batteries

Efficient extraction of electrode components from recycled lithium-ion batteries(LIBs)and their highvalue applications are critical for the sustainable and ecofriendly utilization of resources.This work demonstrates a novel approach to stripping graphite anodes embedded with Li^(+)from spent LIBs directly in anhydrous ethanol which can be utilized as high efficiency cathodes for aluminum-ion batteries(AIBs).Recycled graphite(RG)with foam morphology and crystal structure defects was obtained under the action of ultrasonic peeling and gas generation reaction between residual lithium-graphite interlayer compound and ethanol.The inherent open structure of RG facilitates the intercalation/deintercalation of chloralum anions(AlCl_(4)^(-))and enhances its AIB cathode performance.The electrochemical measurements revea that the RG cathode has a specific capacity of 123 m Ah·g^(-1)at a current of 5 A·g^(-1),which is 1.55 times higher than tha of unprocessed natural graphite and 1.25 times higher than that of commercial artificial graphite.Additionally,the RG cathode demonstrated remarkable stability,retaining its high particular capacity of 138.15 mAh·g^(-1)even through2000 times at 10 A·g^(-1)in a low-cost electrolyte consisting of an ionic liquid/urea/AlCl_(3)mixture.This work offers a novel approach to reusing of graphite anode waste materials from LIBs.

Effects of red-yellow soil acidification on seed germination of Chinese pine

Acid treatments significantly change the physical and chemical properties of red yellow soil by lowering its pH value and leaching out aluminum(Al) ions that are harmful to the growth of plants. The structure of soil will be damaged, resulting in higher viscosity, higher water retention rate and lower air permeability of the soil. The germination rate of Chinese pine( Pinus tabulacformic Carr. ) seeds sowed in soil treated with sulphuric acid(H 2SO 4) decreased compared to that for untreated soil. The direct cause was the large amount of Al ions leached out because of low pH values(≥3.5). The added acid decreased the soil aggregation and increased the number of micro aggregates(under 250 μm in diameter). Such changes increased the soil's viscosity, which tied the pine needles to the soil after the seeds had germinated and prevented the seedlings from fully developing.

Imaging the diffusion pathway of Al^3+ ion in NASICON-type (Al0.2Zr0.8)20/19Nb(PO4)3 as electrolyte for rechargeable solid-state Al batteries

Among all-solid-state batteries, rechargeable Al-ion batteries have attracted most attention because they involve threeelectron-redox reactions with high theoretic specific capacity. However, the solid Al-ion conductor electrolytes are less studied. Here, the microscopic path of Al3+-ion conduction of NASICON-type(Al0.2Zr0.8)20/19Nb(PO4)3oxide is identified by temperature-dependent neutron powder diffraction and aberration-corrected scanning transmission electron microscopy experiments.(Al0.2Zr0.8)20/19Nb(PO4)3shows a rhombohedral structure consisting of a framework of(Zr,Nb)O6octahedra sharing corners with(PO4) tetrahedra; the Al occupy trigonal antiprisms exhibiting extremely large displacement factors. This suggests a strong displacement of Al ions along the c axis of the unit cell as they diffuse across the structure by a vacancy mechanism. Negative thermal expansion behavior is also identified along a and b axes, due to folding of the framework as temperature increases.

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.

Effects of Al^3+on pollutant removal and extracellular polymeric substances(EPS)under anaerobic,anoxic and oxic conditions

Aluminum ions produced by aluminum mining,electrolytic industry and aluminum-based coagulants can enter wastewater treatment plants and interact with activated sludge.They can subsequently contribute to the removal of suspended solids and affect activated sludge flocculation,as well as nitrogen and phosphorus removal.In this study,the effects of Al^3+on pollutant removal,sludge flocculation and the composition and structure of extracellular polymeric substances(EPS)were investigated under anaerobic,anoxic and oxic conditions.Results demonstrated that the highest chemical oxygen demand(COD)and total nitrogen(TN)removal efficiencies were detected for an Al^3+concentration of 10 mg/L.In addition,the maximal dehydrogenase activity and sludge flocculation were also observed at this level of Al^3+.The highest removal efficiency of total phosphorus(TP)was achieved at an Ar+concentration of30 mg/L.The flocculability of sludge in the anoxic zone was consistently higher than that in the anaerobic and oxic zones.The addition of Al^3+promoted the secretion of EPS.Tryptophan-like fluorescence peaks were detected in each EPS layer in the absence of Al^3+.At the Al^3+concentration of 10 mg/L,fulvic acid and tryptophan fluorescence peaks began to appear while the majority of protein species and the highest microbial activity were also detected.Low Al^3+concentrations(<10 mg/L)could promote the removal efficiencies of COD and TN,yet excessive Al^3+levels(>10 mg/L)weakened microbial activity.Higher Al^3+concentrations(>30 mg/L)also inhibited the release of phosphorus in the anaerobic zone by reacting with PO4^3-.

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.

Potassium ion pre‑intercalated MnO_(2)for aqueous multivalent ion batteries

Manganese dioxide(MnO_(2)),as a cathode material for multivalent ion(such as Mg^(2+)and Al^(3+))storage,is investigated due to its high initial capacity.However,during multivalent ion insertion/extraction,the crystal structure of MnO_(2)partially collapses,leading to fast capacity decay in few charge/discharge cycles.Here,through pre-intercalating potassium-ion(K+)intoδ-MnO_(2),we synthesize a potassium ion pre-intercalated MnO_(2),K_(0.21)MnO_(2)·0.31H_(2)O(KMO),as a reliable cathode material for multivalent ion batteries.The as-prepared KMO exhibits a high reversible capacity of 185 mAh/g at 1 A/g,with considerable rate performance and improved cycling stability in 1 mol/L MgSO_(4)electrolyte.In addition,we observe that aluminum-ion(Al^(3+))can also insert into a KMO cathode.This work provides a valid method for modifcation of manganesebased oxides for aqueous multivalent ion batteries.

Flocculating characteristic of activated sludge flocs:Interaction between Al^(3+) and extracellular polymeric substances

Aluminum flocculant can enhance the flocculating performance of activated sludge.However,the binding mechanism of aluminum ion（Al 3＋） and extracellular polymeric substances（EPS） in activated sludge is unclear due to the complexity of EPS.In this work,threedimensional excitation emission matrix fluorescence spectroscopy（3DEEM）,fluorescence quenching titration and Fourier transform infrared spectroscopy（FT-IR） were used to explore the binding behavior and mechanism between Al 3＋ and EPS.The results showed that two fluorescence peaks of tyrosineand tryptophan-like substances were identified in the loosely bound-extracellular polymeric substances（LB-EPS）,and three peaks of tyrosine-,tryptophanand humic-like substances were identified in the tightly boundextracellular polymeric substances（TB-EPS）.It was found that these fluorescence peaks could be quenched with Al 3＋ at the dosage of 3.0 mg/L,which demonstrated that strong interactions took place between the EPS and Al 3＋.The conditional stability constants for Al 3＋ and EPS were determined by the Stern-Volmer equation.As to the binding mechanism,the-OH,N-H,C=O,C-N groups and the sulfurand phosphorus-containing groups showed complexation action,although the groups in the LB-EPS and TB-EPS showed different behavior.The TB-EPS have stronger binding ability to Al 3＋ than the LB-EPS,and TB-EPS play an important role in the interaction with Al 3＋.

A Highly Selective and Sensitive Fluorescent Chemosensor for Detection of Al^(3+) in Totally Aqueous Media

A fluorescent chemosensor(1)based on 2-hydroxy-1-naphthaldehyde Schiff-base was developed for the detec-tion of Al^(3+)in 100%aqueous solution.Upon addition of Al^(3+),a significant fluorescence enhancement was ob-served,which was not affected by other metal ions including Na^(+),K^(+),Ca^(2+),Mg^(2+),Mn^(2+),Co^(2+),Ni^(2+),Cu^(2+),Cr^(3+),Ag+,Pb^(2+),Zn^(2+),Cd^(2+),Hg^(2+),Fe^(2+)and Fe^(3+)under weak acid conditions.Moreover,the specific response to Al^(3+)was visible under natural light.The binding mode between 1 and Al^(3+)was clarified by ESI-MS and 1H NMR.

Synthesis of Highly Stable Porous Metal-lminodiacetic Acid Gels from a Novel IDA Compound

In this work, a novel and simple flexible aromatic multi-carboxylate compound N,N＇（4,4＇-biphenylyl） iminodi- acetic acid （BP-IDA） was synthesized, with which two new stable metaMDA gels （denoted as MIGl and MlG2） with three-dimensional network structures have been prepared successfully by employing Cr^3＋ and Al^3＋ as the metal ions, respectively. The rheological performance was investigated by means of dynamic rheology measurement. The morphology and microstructure were characterized by scanning electron microscopy, transmission elec- tron microscopy, and X-ray diffraction technique. Nitrogen sorption isotherm measurement suggests that the MlG1 aerogel has considerable porosity with the Brunauer-Emmett-Teller specific surface area up to 760 m^2·g^-1. Owing to easy preparation, good stability, and three-dimensional network structure, the as-prepared metal-organic gels will possess potential applications in separation, catalysis, and drug delivery.