Aluminum-ion Batteries Research Articles

Engineering strategies for low-cost and high-power density aluminum-ion batteries

Aluminum-ion batteries (AIBs) for electrochemical energy storage technologies are relatively new research hotspots because of their advantages, such as high theoretical specific capacity, lightweightness, zero pollution, safety, inexpensive and rich resource. Especially, AIBs possess the potential to achieve ultrafast charge and discharge speed because of three-electron redox reactions, becoming the most promising candidate for high power density rechargeable batteries. However, several serious drawbacks, such as passive film formation, anode corrosion, and cathode selection and preparation, hinder the large-scale application of these systems. Here, we introduce the principles of AIBs and review the challenges and outlooks of AIBs from various perspectives, including anode design and protection, electrolyte exploitation and battery design, and cathode selection and preparation. We comprehensively discuss the acquisition of green and low-cost carbonaceous cathode materials with high electrochemical performance. Furthermore, several perspectives on potential research directions for the development of high-power density AIBs are proposed.

Research progress of carbon-based materials in aluminum-ion batteries

Research progress of carbon-based materials in aluminum-ion batteries

Model improvement and SOC estimation based on aluminium ion batteries

The main work of this paper can be divided into three parts: (1) An aluminium ion battery is made, the battery capacity is calibrated under a constant current, and the battery’s voltage and current data under pulse conditions is collected. (2) The influence of the hysteresis effect on the SOC estimation of aluminium ion batteries is fully considered. A model suitable for aluminium ion batteries is established based on the model that the parameter identification and verification was carried out with. (3) The error with the EKF and AEKF algorithms in estimating the SOC of aluminium ion batteries is compared. The experimental results show that the model established in this paper can describe the working state of aluminium ion batteries very well. Compared with the EKF algorithm, the AEKF algorithm is more accurate in estimating the SOC of aluminium ion batteries.

Reversible aluminum ion storage mechanism in Ti-deficient rutile titanium dioxide anode for aqueous aluminum-ion batteries

Aqueous aluminum-ion batteries (AIBs) are potential candidates for future large-scale energy storage devices owing to their advantages of high energy density, resource abundance, low cost, and environmental friendliness. However, the exploration of suitable electrode materials is one of the key challenges for the development of aqueous AIBs. To address this issue, a new Ti-deficient rutile titanium dioxide (Ti0.95□0.05O1.79Cl0.08(OH)0.13) was achieved via univalent ion doping and evaluated as an anode for aqueous AIBs. This material yields a reversible capacity of 143.1 mA h g−1 at 0.5 A g−1. Even at 3 A g−1, an initial reversible charge capacity of 78.3 mA h g−1 can be achieved and retains almost 82% after 110 cycles. The Al3+ ion storage mechanism has been intensively investigated by ex-situ XRD, XPS, SEM, TEM and Raman techniques, indicating that Al3+ ions can reversibly insert into Ti vacancies and lattice of the Ti0.95□0.05O1.79Cl0.08(OH)0.13 without phase change, leading to much enhanced capacity as compared to the commercial rutile TiO2. These results demonstrate that cationic defect engineering is an effective strategy to improve the electrochemical properties of electrode materials for aqueous AIBs.

Designing electrode materials for aluminum-ion batteries towards fast diffusion and multi-electron reaction

From a computational perspective, to improve the incomplete multi-electron reaction and slow dynamics of aluminum ions, two highlighted strategies are put forward, namely, developing aluminous compounds, and selecting highly symmetrical structures for electrode materials.

Dealloying: An effective method for scalable fabrication of 0D, 1D, 2D, 3D materials and its application in energy storage

Nanomaterials have promising applications in catalysis, filtration, hydrogen storage, sensors, automobile exhaust treatment, and energy storage and conversion, etc. However, scalable and economic fabrication of nanomaterials remains a challenge. In the past century, the world has witnessed successful industrialization of nanoporous Raney nickel in thousands of tons per year by dealloying method. With the advantages of low cost, scalable fabrication and controllable structure, dealloying technique has attracted more attention and gained wider applied in numerous areas. This review attempts to summarize the recent progress in development of dealloying technique, with special emphasis on synthetic materials (0D, 1D, 2D, 3D) and advanced applications, including lithium-ion batteries, lithium-oxygen batteries, lithium-sulfur batteries, lithium-metal batteries, zinc-metal batteries, sodium-ion batteries, magnesium-ion batteries, potassium-ion batteries, aluminum-ion batteries, aluminum-carbon dioxide batteries, and supercapacitors, etc. The advantages, theoretical research, and influence factors of dealloying technique are also analyzed. Besides, key scientific issues and prospective directions of dealloying technique are also discussed. We believe this review may attract more researchers in relevant fields and offer some guide for the future development of dealloying technique.

Roadmap on Ionic Liquid Electrolytes for Energy Storage Devices.

Ionic liquids are considered to be promising electrolyte solvents or additives for rechargeable batteries (i. e., lithium-ion batteries, sodium-ion batteries, lithium-sulfur batteries, aluminum-ion batteries, etc.) and supercapacitors. This is related with the superior physical and electrochemical properties of ionic liquids, which can influence the performance of rechargeable batteries. Therefore, it is necessary to write a roadmap on ionic liquids for rechargeable batteries. In this roadmap, some progress, critical techniques, opportunities and challenges of ionic liquid electrolytes for various batteries and supercapacitors are pointed out. Especially, properties and roles of ionic liquids should be considered in energy storage. Ionic liquids can be used as electrolyte salts, electrolyte additives, and solvents. For optimizing ionic liquid-based electrolytes for energy storage, their applications in various energy storage devices should be considered by combing native chemical/physical properties and their roles. We expect that this roadmap will give a useful guidance in directing future research in ionic liquid electrolytes for rechargeable batteries and supercapacitors.

9,10-Anthraquinone/K2CuFe(CN)6: A Highly Compatible Aqueous Aluminum-Ion Full-Battery Configuration

Temporally intermittent and spatially dispersed renewable energy sources strongly call for large-scale energy storage devices. Aqueous aluminum-ion batteries show great potential for application due to their safety and low cost. Thus far, however, the ideal full-battery configuration is beyond the scope due to shortcomings with regards to suitable anode and cathode materials. Herein, we report a pioneering aqueous aluminum-ion battery system consisting of a Prussian white cathode, 1 M Al2(SO4)3 aqueous electrolyte, and an organic 9,10-anthraquinone anode. The oxidation capability of the Prussian white cathode during the first charging allows for the fabrication of the full battery without pre-inserting aluminum ions, thus making the rocking-chair-type battery feasible. Importantly, the open-framework structure of the Prussian white and distinct enolization charge storage mechanism of 9,10-anthraquinone ensure fast reaction kinetics. The full battery exhibits cycling stability with a capacity retention of 89.1% over 100 cycles at 500 mA g-1, finishing a cycle in about 10 min. This work provides a pathway for developing rechargeable aqueous aluminum-ion batteries.

Fast and stable K-ion storage enabled by synergistic interlayer and pore-structure engineering

Carbon-based material has been regarded as one of the most promising electrode materials for potassium-ion batteries (PIBs). However, the battery performance based on reported porous carbon electrodes is still unsatisfactory, while the in-depth K-ion storage mechanism remains relatively ambiguous. Herein, we propose a facile “in situ self-template bubbling” method for synthesizing interlayer-tuned hierarchically porous carbon with different metallic ions, which delivers superior K-ion storage performance, especially the high reversible capacity (360.6 mAh·g−1@0.05 A·g−1), excellent rate capability (158.6 mAh·g−1@10.0 A·g−1) and ultralong high-rate cycling stability (82.8% capacity retention after 2,000 cycles at 5.0 A·g−1). Theoretical simulation reveals the correlations between interlayer distance and K-ion diffusion kinetics. Experimentally, deliberately designed consecutive cyclic voltammetry (CV) measurements, ex situ Raman tests, galvanostatic intermittent titration technique (GITT) method decipher the origin of the excellent rate performance by disentangling the synergistic effect of interlayer and pore-structure engineering. Considering the facile preparation strategy, superior electrochemical performance and insightful mechanism investigations, this work may deepen the fundamental understandings of carbon-based PIBs and related energy storage devices like sodium-ion batteries, aluminum-ion batteries, electrochemical capacitors, and dual-ion batteries.

Ultra-fast charging in aluminum-ion batteries: electric double layers on active anode

With the rapid iteration of portable electronics and electric vehicles, developing high-capacity batteries with ultra-fast charging capability has become a holy grail. Here we report rechargeable aluminum-ion batteries capable of reaching a high specific capacity of 200 mAh g−1. When liquid metal is further used to lower the energy barrier from the anode, fastest charging rate of 104 C (duration of 0.35 s to reach a full capacity) and 500% more specific capacity under high-rate conditions are achieved. Phase boundaries from the active anode are believed to encourage a high-flux charge transfer through the electric double layers. As a result, cationic layers inside the electric double layers responded with a swift change in molecular conformation, but anionic layers adopted a polymer-like configuration to facilitate the change in composition.

Polythiophene/Carbon Microsphere Composite as a High-performance Cathode Material for Aluminium-ion Batteries

Due to the high theoretical volume specific capacity and mass specific capacity of aluminum-ion batteries, they can meet the needs of contemporary society for high-performance energy storage devices, and have attracted a lot of research strength. Cathode materials are a key issue limiting the development of aluminum-ion batteries. Herein, polythiophene was prepared on the surface of carbon microspheres by in-situ oxidative polymerization, resulting in polythiophene carbon microsphere composite materials. It exhibits excellent electrochemical performance, as a cathode material for aluminum-ion batteries, in terms of a high specific capacity (106 mAh g−1 at a current density of 1 A g−1), good stability (maintaining 58 % of initial capacity after 10000 cycles) and excellent rate performance (90 mAh g−1 at a high current density of 3.5 A g−1).

Cation-synergy stabilizing anion redox of Chevrel phase Mo6S8 in aluminum ion battery

Anion redox chemistry is an essential component of many high energy density electrode materials, while accompanying with voltage hysteresis and fade, which currently hinders its widespread use. Here we demonstrate cation-synergy stabilizing anion redox of Chevrel phase Mo6S8 in aluminum ion battery. EELS and XAS reveal that S is fully reduced, and Mo6 cluster is firstly oxidized and then reduced with Al3+ ions insertion, which originates from the contraction and elongation of Mo-Mo bond in Mo6 cluster verified by atomic-resolved imaging. DFT calculations uncover that the energy level of [Mo-Mo]* antibonding orbitals is lifted and fell by Mo-Mo bond evolution, resulting in the synergetic cationic and anionic redox, which contributes to the stable structure upon cycling. Our work figures out the electrochemical redox mechanism of Mo6S8 in aluminum ion batteries and provides implications generally for the design of materials employing anion redox chemistry.

Rechargeable Aqueous Aluminum Organic Batteries.

Aqueous aluminum-ion batteries (AABs) are regarded as promising next-generation energy storage devices, and the current reported cathodes for AABs mainly focused on inorganic materials which usually implement a typical Al3+ ions (de)insertion mechanism. However, the strong electrostatic forces between Al3+ and the host materials usually lead to sluggish kinetics, poor reversibility and inferior cycling stability. Herein, we employ an organic compound with redox-active moieties, phenazine (PZ), as the cathode material in AABs. Different from conventional inorganic materials confined by limited lattice spacing and rigid structure, the flexible organic molecules allow a large-size Al-complex co-intercalation through reversible redox active centers (-C=N-) of PZ. This co-intercalation behavior can effectively reduce desolvation penalty, and substantially lower the Coulombic repulsion during the ion (de)insertion process. Consequently, this organic cathode exhibits a high capacity and excellent cyclability, which exceeds those of most reported electrode materials for AABs. This work highlights the anion co-intercalation chemistry of redox-active organic materials, which is expected to boost the development of high-performance multivalent-ion battery systems.

Construction of Interlayer-Expanded MoSe2/Nitrogen-Doped Graphene Heterojunctions for Ultra-Long-Cycling Rechargeable Aluminum Storage

Owing to their low cost and abundant reserves, aluminum-ion batteries (AIBs) have been considered a potential candidate for future large-scale storage applications. However, AIBs are still in the s...

N-doped C@ZnSe as a low cost positive electrode for aluminum-ion batteries: Better electrochemical performance with high voltage platform of ~1.8 V and new reaction mechanism

Rechargeable aluminum-ion batteries (AIBs) are being extensively studied as a promising battery system due to their abundant resources and high theoretical capacity. However, the lack of suitable positive electrode materials with high electrochemical performances limits their practical application. Herein, a novel N-doped porous carbon/ZnSe composite (NC@ZnSe) with ZnSe nanoparticles evenly dispersed porous carbon derived from pyrolysis and selenization of ZIF-8 has been prepared for AIBs. The AIBs based on NC@ZnSe positive electrode not only deliver a high discharge specific capacity of 172.7 mAh g−1, but also provide a high discharge plateau at ~1.8 V vs. Al/Al3+, which is one of highest discharge plateaus for a transition metal chalcogenides electrode. Besides, Al/NC@ZnSe batteries present excellent cyclic stability with discharge specific capacity exceeds 70 mAh g−1 retained at 500 mA g−1 after 250 cycles. More importantly, the storage aluminum of NC@ZnSe is based on the conversion-alloying reaction mechanism, which is significantly different from the previously reported conversion or intercalation storage energy mechanism in AIBs. Therefore, the superior storage Al3+ performance of NC@ZnSe may be due to its unique conversion-alloying reaction mechanism. This work demonstrates that NC@ZnSe is a low-cost, naturally abundant, environmentally friendly electrode materials with high electrochemical performances for AIBs.

High-performance wire-shaped aluminum ion batteries based on continuous graphene fiber cathodes

Due to their high capacity and cyclic stability, aluminum ion battery (AIB) shows great potential to be used as efficient energy storage system for various electronics. However, the aluminum ion batteries with a typical planar structure greatly limit their practical applications in the fields of flexible and wearable electronics towards intelligence, miniaturization and portability. Herein, we demonstrate a novel wire-shaped aluminum ion battery, which is fabricated with graphene fiber (GF) as cathode and aluminum (Al) wire as anode. The developed Al/GF battery not only delivers a high specific capacity of 115 mAh g−1, but also exhibits excellent rate capability and cycling stability after 1000 charge-discharge under high current density of 50 A g−1. Due to the unique structure, the developed wire-shaped battery can well maintain their original electrochemical performance under different bending states and even after hundreds of bending cycles, suggesting outstanding mechanical flexibility and stability. The flexible wire-shaped aluminum ion battery is a promising candidate to be used as power supplies for flexible and portable electronics.

Gel Polymer Electrolyte for Aluminum-Ion Batteries

Aluminum-based batteries have potential advantages such as low flammability, low cost, and 3 electrons in the reaction that give them high charge capacity. Current research focuses on aluminum-ion batteries with carbon-derived cathodes that have achieved fast-charge capability and long-term stability; however, present some problems as: the disintegration of the cathodic material, the use of ionic liquids electrolytes, whose corrosivity, sensitivity to the environment and cost, generate safety and design problems for commercial devices. An aluminum-ion polymer battery was constructed with aluminum foil anode, graphene paper cathode, and an iongel of PMMA-AlCl3(0.68)-EMIm|AlCl4(80%) as the electrolyte, to reduce the environmental sensitivity and achieve different types of assembly. The battery was evaluated using Cyclic Voltammetry and Electrochemical Impedance Spectroscopy (EIS), finding reversible behavior between 1.5V-2.5V vs. Al (QRE) associated with the plasticizer reaction and irreversible reduction peaks between 0.5V-1.5V vs. Al (QRE) produced by the coordination of chloroaluminate cations with the polymer matrix. The battery presented a maximum coulombic efficiency of ~60%, the losses are attributed to the cathode collector corrosion and the irreversibilities in the electrodes.

Activated carbon derived from coconut shell chars for use as a cathode material in aluminium-ion batteries

Aluminium-ion batteries (AIBs) are a promising energy storage system due to their significant advantages of low cost, high anode capacity and safety. Nevertheless, the critical challenge limiting AIB performance is an inadequate cathode capacity that diminishes their cell energy density. To overcome this limitation, it is important to develop novel cathode materials with high cathode capacity for AIBs. Herein, we report an activated carbon derived from coconut shell chars for use as a cathode material in AIBs. The activated carbon was synthesized via KOH activation and carbonization. The prepared cathode material exhibits a high specific capacity of 38 mAh g−1 at a high current density of 1 A g−1 due to its high specific surface area of 2686 m2 g−1, which is beneficial for chloroaluminate-ion accommodation. This result indicates that the activated carbon derived from coconut shell chars with its high surface area is electrochemically active and is likely to be a promising cathode material for AIBs.

Ionic Liquid-Based Electrolytes for Aluminum/Magnesium/Sodium-Ion Batteries

Developing post-lithium-ion battery technology featured with high raw material abundance and low cost is extremely important for the large-scale energy storage applications, especially for the metal-based battery systems such as aluminum, sodium, and magnesium ion batteries. However, their developments are still in early stages, and one of the major challenges is to explore a safe and reliable electrolyte. An ionic liquid-based electrolyte is attractive and promising for developing safe and nonflammable devices with wide temperature ranges owing to their several unique properties such as ultralow volatility, high ionic conductivity, good thermal stability, low flammability, a wide electrochemical window, and tunable polarity and basicity/acidity. In this review, the recent emerging limitations and strategies of ionic liquid-based electrolytes in the above battery systems are summarized. In particular, for aluminum-ion batteries, the interfacial reaction between ionic liquid-based electrolytes and the electrode, the mechanism of aluminum storage, and the optimization of electrolyte composition are fully discussed. Moreover, the strategies to solve the problems of electrolyte corrosion and battery system side reactions are also highlighted. Finally, a general conclusion and a perspective focusing on the current development limitations and directions of ionic liquid-based electrolytes are proposed along with an outlook. In order to develop novel high-performance ionic liquid electrolytes, we need in-depth understanding and research on their fundamentals, paving the way for designing next-generation products.

Investigation of Al(TfO)3-based deep eutectic solvent electrolytes for aluminium-ion batteries. Part I: understanding the positively charged Al complex formation.

Aluminium-ion batteries (AIB) are very attractive energy storage systems due to the high availability and theoretical energy density of metallic aluminium. However, the practical performance of AIBs in AlCl3-based electrolytes is limited by the low reversible capacity of the positive graphite electrode for large AlCl4- anions. Moreover, the use of high energy oxide-based electrodes such as MnO2 requires the presence of positively charged aluminium complexes in the electrolyte. In this work, the coordination of Al complexes in deep eutectic solvents (DESs) composed of Al triflate Al(TfO)3 as the conducting salt, urea and/or acetamide as the hydrogen bond donor and formamide and N-methylacetamide as the solvent was investigated. Both solvents were able to dissolve and dissociate Al(TfO)3 principally to a single positively charged Al complex [Al(TfO)2-solventn]+ which was confirmed by Raman and NMR spectroscopy analyses. Furthermore, the addition of urea led to further dissociation to the [AlTfO-solventn-urea2]2+ complex that can be assigned to the bidentate hydrogen bonding of urea with TfO at a specific ratio of urea/Al(TfO)3 of 4 : 1. Because of their partial miscibility with urea, other conventional solvents such as propylene carbonate and acetonitrile dissociate Al(TfO)3 only once to form [AlTfO2-solventn]+. The as-prepared formamide and N-methylacetamide-based DES electrolytes show good conductivity values of 9.65 and 2.45 mS cm-1, respectively.