Rechargeable Aluminum-ion Batteries Research Articles

In situ growth of metal–organic framework-derived CoTe2 nanoparticles@nitrogen-doped porous carbon polyhedral composites as novel cathodes for rechargeable aluminum-ion batteries

Rechargeable aluminum-ion batteries (AIBs) have attracted widespread attention due to their high theoretical capacity, abundant aluminum resources, high safety and low cost.

DFT simulation of the X-ray diffraction pattern of aluminum-ion-intercalated graphite used as the cathode material of the aluminum-ion battery

Many breakthroughs have been achieved in rechargeable aluminum-ion battery technologies in recent years. Most recently, operando X-ray diffraction (XRD) combined with density functional theory (DFT) calculations was reported to study the chloroaluminate anion (AlCl4-)-intercalated graphite cathode of the battery. However, there are quite a few discrepancies between the measured and simulated XRD patterns. This work is focused on the simulation of XRD patterns of graphite intercalation compounds (GICs) with DFT calculations. Our results reveal that both the geometry of AlCl4- in graphite and the gallery height of GICs are dependent on the intercalant density. At low intercalant density, the gallery height keeps constant, but at high intercalant densities, the gallery height is linearly related to the intercalant density. Our simulated XRD patterns are highly consistent with the measured operando XRD patterns. Not only do the angles of the peaks match very well, but also the relative intensities and the corresponding electrode capacities show reasonable agreement with the experimental results. The DFT simulation of the XRD pattern provides significant information on the stage index and the charge capacity of the GIC electrode.

The molten chlorides for aluminum-graphite rechargeable batteries

A low-cost, high-capacity Al-graphite rechargeable aluminum-ion battery is confirmed to be able to work stably in a quaternary AlCl3-NaCl-LiCl-KCl inorganic molten salt as electrolyte with the lowest eutectic temperature of less than 75 °C. The battery shows a stable specific capacity of 114.9 mAh g−1 at 200 mA g−1 over 1500 cycles at 90 °C. Moreover, the capacity can remain at ∼85 mAh g−1 with a higher current density of 800 mA g−1 over 2600 cycles at 90 °C. Importantly, even cycled at 80 °C and 100 °C, almost 100% capacity retention can be achieved after 5800 cycles when the temperature is back to 90 °C, verifying the superior long-term cycling stability under various temperatures. The inherent low-cost and high capacity, as well as outstanding long-term cycling stability, makes it particularly favorable for large-scale energy storage devices.

Metal-organic framework-derived metal oxide nanoparticles@reduced graphene oxide composites as cathode materials for rechargeable aluminium-ion batteries

The use of metal oxides as electrode materials has seen great success in lithium-ion batteries. However, this type of electrode materials has been regarded as an improper option for rechargeable aluminium-ion batteries (AIBs) in comparison with sulfides and selenides, and has, thus, been nearly abandoned. Here, we demonstrate the suitability of metal oxides as cathode materials of AIBs, exhibiting high electrochemical activities toward Al-ion storage. We designed economical metal-oxide cathodes (Co3O4@reduced graphene oxide (rGO), Fe2O3@rGO, and CoFe2O4@rGO) for AIBs. The Co3O4@rGO displayed superior electrochemical properties, regarding both capacity and lifespan, to the current state-of-the-art cathode material reported by scientific literature. Furthermore, the CoFe2O4@rGO exhibits rational electrochemical capacities and an extremely stable charge/discharge process with an excellent Coulombic efficiency of 99.6%. The proposed study expects to stimulate researchers to focus on the overlooked metal oxides as competitive cathode materials for high performance AIBs.

Graphite carbon-encapsulated metal nanoparticles derived from Prussian blue analogs growing on natural loofa as cathode materials for rechargeable aluminum-ion batteries

Aluminum-ion batteries (AIBs) are attracting increasing attention as a potential energy storage system owing to the abundance of Al sources and high charge density of Al3+. However, suitable cathode materials to further advance high-performing AIBs are unavailable. Therefore, we demonstrated the compatibility of elemental metal nanoparticles (NPs) as cathode materials for AIBs. Three types of metal NPs (Co@C, Fe@C, CoFe@C) were formed by in-situ growing Prussian blue analogs (PBAs, Co[Co(CN)6], Fe[Fe(CN)6] and Co[Fe(CN)6]) on a natural loofa (L) by a room-temperature wet chemical method in aqueous bath, followed by a carbonization process. The employed L effectively formed graphite C-encapsulated metal NPs after heat treatment. The discharge capacity of CoFe@C was superior (372 mAh g−1) than others (103 mAh g−1 for Co@C and 75 mAh g−1 for Fe@C). The novel design results in CoFe@C with an outstanding long-term charge/discharge cycling performance (over 1,000 cycles) with a Coulombic efficiency of 94.1%. Ex-situ X-ray diffraction study indicates these metal NP capacities are achieved through a solid-state diffusion-limited Al storage process. This novel design for cathode materials is highly significant for the further development of advanced AIBs in the future.

Properties of CoS2/CNT as a Cathode Material of Rechargeable Aluminum-Ion Batteries

Aluminum ion batteries (AIBs) are considered, in principle, promising post-lithium-ion batteries, which are potential for using in grid-scale energy storage and electric vehicles, owing to the economic Al. The inflammable ionic liquid electrolyte endows stable plating and stripping of Al ions. A spotlighted research on cathode material has been preforming to obtain a high-performance cathode material that can match well with the prominent Al foil. However, one over-looked factor for the study of cathode materials is the cost and possibility of mass-production. With this key point in mind, we as the forerunner studied the CoS2/carbon nanotubes (CNTs) composite cathode material composed of low cost and commercialized CoS2 and multi-wall CNTs to promote the development of AIBs. Stable charge/discharge plateaus (at 1.2/0.9 V vs. AlCl4−/Al) during cycling test were obtained for the CoS2/CNTs product at a high current density of 1000 mA g−1, with an extremely high Coulombic efficiency of 98% and reasonable electrochemical capacities. This report is expected to contribute more contribution in the development of cathode materials for rechargeable AIBs.

S@GO as a High-Performance Cathode Material for Rechargeable Aluminum-Ion Batteries

Aluminum-ion batteries (AIBs) are considered promising post lithium-ion batteries owing to their outstanding safety, gravimetric and volumetric capacities, and cost efficiency advantages. However, one practical obstacle to their development is the lack of reliable cathode materials that can be coupled with the distinguished Al anode. To address this issue, we synthesized a S@GO composite material for use as a cathode material in AIBs. The synthesized S@GO material exhibits a rod structure with a diameter of around 100 nm. Inside these nanorods, sulfur nanoparticles with a size of around 5 nm were uniformly anchored on the graphene sheets. By taking the advantage of an introduction of graphene sheets, the capacities were significantly preserved, displaying a capacity that was more than double that of a bare S active material. In addition, a 3000-cycle long-term repeated charge/discharge measurement exhibited extremely stable capacity values with a high Coulombic efficiency of 98% at the 3000th cycle. The charge/discharge processes were clearly shown during the repeated cycling measurement at a high current density of 1000 mA g−1. This work is expected to stimulate further study of elemental S used as a cathode material for high-performance AIBs.

Two-dimensionally porous cobalt sulfide nanosheets as a high-performance cathode for aluminum-ion batteries

Rechargeable aluminum-ion batteries (AIBs) are regarded as a great potential developing energy storage device with the advantages of abundant resources, high theoretical specific capacity and high safety. Nevertheless, the scarcity of suitable cathode materials with satisfactory rate performance and cycling stability hinders its further development and wider field of application. Here, we demonstrate a strategy for designing a novel two-dimensionally porous Co9S8 nanosheets as the cathode materials for AIBs. The electrode exhibits an outstanding electrochemical performance with an excellent cycling stability (maintains 120 mAh g−1 after 250 cycles at 0.2 A g−1) and enchanced rate performance (60 mAh g−1 at 2 A g−1 and can quickly recover to 120 mAh g−1 when the current density is reduced back to 0.1 A g−1). Furthermore, high capacity retentions and superior stability for the assembled soft-pack batteries can also be achieved under high and low temperatures and stringent bending conditions. The remarkable aluminum storage behavior of the engineered Co9S8 cathode is attributed to its unique two dimensional (2D) geometrical architecture, abundant internal porosity and nanosized secondary building blocks. Our findings appear to provide a potential new avenue in the design of cathode materials in AIBs.

Thick electrodes upon biomass-derivative carbon current collectors: High-areal capacity positive electrodes for aluminum-ion batteries

Rechargeable aluminum-ion batteries (AIBs) are considered as low-cost safe energy storage devices beyond lithium-ion batteries, due to the high volumetric capacity and rich abundance of aluminum. However, the highly corrosive room temperature ionic liquid electrolyte causes serious problems in the traditional metal current collectors, and electrochemical inert metals with higher density have been commonly used, which leads to dramatic decreased material utilization in the positive electrode. For addressing such issues, here a biomass-derivative carbon (BDC) current collector is demonstrated to construct millimeter-scale thick positive electrodes based on two types of graphite active materials (with different planar sizes) and two electrode configurations. The results suggest the strategy of using single-side casting process with graphite of smaller planar size would be more promising to promote the overall electrochemical properties and energy storage performance. The as-assembled thick electrode (with thickness up to ∼2 mm) using the same type of graphite is able to deliver much enlarged areal loading (36 mg cm−2), showing greater areal capacity for energy storage. The strategy and mechanism in this work offers a considerable approach for improving the current collectors and promoting the graphite proportion in AIBs.

Dual Storage Mechanism Induced High Capacity Cathode for Rechargeable Aluminium Ion Battery

Rechargeable energy storage devices have attained much interest in the society as it provides solution to energy crisis. The excessive use of lithium due to ever increasing demand of lithium ion battery in stationary energy storage and portable electronic devices coupled with restricted availability, urges to move towards alternative low cost energy storage device. Developing a new type of sustainable electrochemical energy storage device depends on the exploration of electrochemistry of other alkali metals. Looking for the low cost energy storage device, Al is the third most abundant element in the Earth’s crust and can be used as low cost energy storage device. Moreover, it can exchange three redox electrons per cations so that the energy density of the battery is high compared to lithium based storage system. But the lack of suitable cathode material is the major draw back of aluminium ion battery not reaching the level of commercialization. Carbon based materials like graphite and reduced graphene oxide have been probed as a cathode material where the charge storage occurs by the in intercalation of AlCl4 - anion into the graphite interlayer which limits the specific capacity in the range of 80 to 100 mAh g-1. Cathode materials, which can also intercalate trivalent aluminium ions, can enhance the specific capacity. This work aims to design a cathode material, which can react with both Al3+ and AlCl4 – ions. Sulfur, a cost effective material, embedded in distorted multiwalled carbon nanotubes (DCNT) provides a new concept of both intercalation of AlCl4 – ions in DCNT as well as conversion reaction of sulfur with trivalent aluminium ions. This design of cathode delivers a specific capacity of 500 mAh g-1 at a current density of 50 mA g-1 with a stable cycling of about 600 cycles and can lead to the development of high energy density rechargeable aluminium ion battery.

Ordered Macro-Microporous Metal-Organic Framework Single Crystals and Their Derivatives for Rechargeable Aluminum-Ion Batteries.

Constructing ordered hierarchical porous structures while maintaining their overall crystalline order is highly desirable but remains an arduous challenge. Herein, we successfully achieve the growth of single-crystalline metal-organic frameworks (MOFs) in three-dimensional (3D) ordered macroporous template voids by a saturated solution-based double-solvent-assisted strategy with precise control over the nucleation process. The as-prepared single-crystalline ordered macro-microporous Co-based MOFs (SOM ZIF-67) exhibit an ordered macro-microporous structure with robust single-crystalline nature. Moreover, SOM ZIF-67 can serve as a precursor to derive 3D-ordered macroporous cobalt diselenide@carbon (3DOM CoSe2@C) through a facile carbonization-selenization treatment. The as-derived 3DOM CoSe2@C can well preserve the 3D-ordered macroporous structure of the precursor. More importantly, CoSe2 nanoparticles could be uniformly confined in the conductive ordered macroporous carbon framework, affording regularly interconnectedmacroporous channels and large surface area. As a result, when evaluated as a cathode material for aluminum-ion batteries, the ordered macroporous structure could not only effectively facilitate the diffusion of large-sized chloroaluminate anions but also increase the contact area with electrolyte and provide more exposed active sites, thereby exhibiting superior reversible rate capacity (86 mA h g-1 at 5.0 A g-1) and remarkable cycling performance (125 mA h g-1 after 1000 cycles at 2.0 A g-1).

Binder-free ultrasonicated graphite flakes@carbon fiber cloth cathode for rechargeable aluminum-ion battery

Aluminum battery offers a new possibility for low cost and large-scale stationary storage of electricity because it can be made with cheap materials and exhibits high theoretical mass specific capacity and power density. Among many cathodic materials, graphite/graphene may be one of the most promising cathode materials for aluminum-ion battery. A suitable three-dimensional structure of the cathode is an important factor for the high performance of battery. In this paper, a binder-free cathode is prepared by dropcasting small ultrasonicated graphite flakes (u-GF) on carbon fiber cloth (CFC) which provides a three-dimensional network skeleton for the new cathode. Al|EMImCl-1.3AlCl3|u-GF@CFC battery exhibits a high discharge specific capacity of ~140 mAh g−1 at 100 mA g−1. The battery has good rate performance and cycling stability: the capacity still exceeds 100 mAh g−1 at 600 mA g−1 with a high coulomb efficiency of 98% and maintains 60 mAh g−1 at 3000 mA g−1 over 300 cycles.

Electrochemical study on the rechargeability of TiO2 as electrode material for Al-ion batteries with chloroaluminate ionic liquid electrolyte

The renewal of research interest in rechargeable aluminum-ion batteries could be seen as a massive boost for the exploration of Al3+-ion electroactive electrode materials in recent times. Titanium dioxide (TiO2) is less explored but could be a promising electrode material for aluminum-ion battery. Here, we demonstrate the rechargeability of an Al-ion cell with anatase TiO2 as cathode in chloroaluminate ionic liquid electrolyte. The Al-TiO2 cell exhibited excellent long-term stability with maximum specific capacity of 25 mAh g−1 at current rate of 500 mA g−1 at room temperature. The electroactive nature of TiO2 in the chloroaluminate electrolyte is clearly demonstrated both by cyclic voltammetry and galvanostatic cycling studies. The synergistic effect of current collector in improving the long-term stability of Al-TiO2 cell is also revealed.

Real-Time Imaging Analysis on Dendrite Formation of Aluminium Metal Anodes

In recent years, rechargeable batteries are one of the most attractive options for both grid electrical energy storage and electrical vehicle (EV) applications due to the steadily increasing demands. Aluminum is the most abundant metal in the earth’s crust. Rechargeable aluminum-ion batteries (AIBs) is a promising research for future energy storage technologies due to its impressive advantages such as high anode capacity (gravimetric capacity of 2980 mAh g−1, and volumetric capacity of 8040 mAh cm−3), cost effectiveness, and safety. A recent study reported by Dai et al. cooperate with ITRI opened a new stage for this topic by employing an AlCl3/[EMIm]Cl ionic liquid electrolyte and graphitic cathode. This pioneering work has been stimulating various research enthusiasms in aluminum-ion batteries (AIBs). At present, there are multiple challenges that need to be overcome in AIBs, including, for example, decomposition of the electrolyte material, small charge-discharge voltage window of the battery, and small energy/power densities, (compared with commercially available lithium batteries). The occurrence of aluminum dendrites, which could cause safety hazards, on the other hand, has not drawn sufficient attention. In this study, we studied in real-time using optical microscopy the occurrence of dendritic aluminum electrochemical plating and its dendrite formation mechanisms. In particular, extensive real-time optical microscopy imaging and post mortem SEM analyses are carried out in conjunction with electrochemical characterizations to reveal the underlying mechanisms for the resulting effects. Figure 1

Graphene aerogel derived compact films for ultrafast and high-capacity aluminum ion batteries

Rechargeable aluminum ion batteries (AIBs) with low cost and nonflammability have attracted considerable interest for electronics and grid energy storage, however, developing densely-compact cathodes, with rapid ion/electron transport channels and high energy storage capability remains challenging. Herein, we reported the facile construction of the nanoporous densely-stacked films derived from three-dimensional (3D) graphene aerogels, prepared by the self-propagating combustion rapid reduction of graphene oxide aerogels within seconds, as advanced binder-free cathode for ultrafast and high-capacity AIBs. Owing to the notable characteristics of 3D interconnected yet nanoporous structure, large surface area (513 m2 g−1), high electrical conductivity (581 S cm−1), dense stacking (0.61 g cm−3), expanded interlayer spacing (3.69 Å) of graphene aerogel-derived compact film, the as-assembled AIBs deliver considerably high capacity of 245 mAh g−1 at 1 A g−1, at least twice of graphite for AIBs. Impressively, our AIBs display exceptional rate capability, showing 70 mAh g−1 at a high current density of 15 A g−1, coupled with superior cycling stability without obvious capacity decay after 5000 times, and wide temperature operation from 0 to 60 °C, outperforming most reported carbon based cathodes for AIBs.

Flexible Free-Standing MoS2/Carbon Nanofibers Composite Cathode for Rechargeable Aluminum-Ion Batteries

Rechargeable aluminum-ion batteries are considered promising candidates for the new generation of energy storage systems because of their high capacity, low cost, and high security. The most urgent...

Preparation and in-situ Raman characterization of binder-free u-GF@CFC cathode for rechargeable aluminum-ion battery

We provide a method for preparation of binder-free cathode for rechargeable aluminum-ion batteries (AIBs). Ultrasonicated natural graphite (u-NG) flakes in N-methylpyrrolidone (NMP) is drop-casted to a carbon fiber cloth (CFC) to obtain binder-free u-GF@CFC cathode for AIBs. We also provide an in-situ Raman spectral technology and the corresponding in-situ Raman cell to determine the mechanism of intercalation/deintercalation reactions of the chloroaluminate ions at cathode of AIBs. The in-situ Raman spectra are recorded using a Raman spectrometer combined with a potentiostat/galvanostat model electrochemical workstation.•A simple preparation method of a binder-free u-GF@CFC cathode is suggested.•The u-GF@CFC cathode is obtained by drop-casting ultrasonicated graphite flakes on the surface and internal gaps of the carbon fiber cloth.•The method includes the in-situ Raman spectral technology and the corresponding in-situ Raman cell.

A critical perspective on rechargeable Al-ion battery technology.

The development of rechargeable aluminum-ion batteries (AIBs) has recently attracted much scientific attention due to the low cost and high specific capacity of Al. Most efforts are being concentrated on enhancing the specific charge capacity of active materials for the positive electrode, while other important issues for commercial deployment of this technology have often been overlooked. The aim of this frontier article is not to systematically review the recent advances in the literature, but to bring under the spotlight the critical aspects requiring intensive research activity for paving the way toward the commercialization of AIBs. After a brief revision of the fundaments of an Al-ion battery, the discussion is classified into 5 sections: energy density, specific power, cost, cycle life and safety. Finally, a performance comparison among Al-ion, Li-ion and lead-acid battery technologies on the basis of these 5 primary parameters summarizes the strengths and limitations of Al-ion batteries.

The potential application of black and blue phosphorene as cathode materials in rechargeable aluminum batteries: a first-principles study.

Developing a suitable cathode material for rechargeable aluminum-ion batteries (AIBs) is currently recognized as a key challenge in pushing AIBs from lab-level to industrial application. Herein, detailed density functional theory (DFT) calculations are carried out to investigate the potential application of black and blue phosphorus monolayers as cathode materials for AIBs. It can be found that AlCl4- ions can strongly bind with both phosphorene allotropes, along with significant charge transfer. For black P, a semiconducting-to-metallic transition is realized in the (AlCl4)8P16 compound. Likewise, the band gap of blue P is reduced from 1.971 eV (pristine blue P) to 0.817 eV. Moreover, both phosphorene allotropes show excellent structural integrity with increased AlCl4- concentration, while delivering competitive theoretical capacities of 432.29 and 384.25 mA h g-1 for black ((AlCl4)8P16) and blue phosphorene ((AlCl4)8P18), respectively. Kinetic calculations present modest energy barriers of 0.19 and 0.39 eV for AlCl4- ions migrating on the surface of black and blue P, and an anisotropic migration nature is also found in both phosphorene allotropes. Based on our results, black and blue phosphorene show great potential as cathode materials for AIBs with robust ion-adsorption, insignificant deformation, self-improved conductivity, and fast kinetic performance.

Cu3P as a novel cathode material for rechargeable aluminum-ion batteries

This paper reports that Cu3P is capable of delivering high specific capacity as the cathode material for rechargeable aluminum-ion batteries.