Rechargeable Aluminum-ion Batteries Research Articles

Poly(3-Methylthiophene)/Graphene Composite Cathode for Rechargeable Aluminum-Ion Batteries.

To reduce the dependence on traditional fossil energy, developing efficient energy storage systems is urgent. The reserves of aluminum resources in the earth's crust are extremely rich, which makes aluminum-ion batteries a promising competitor of new energy storage devices. Here, we report a poly(3-methylthiophene)/graphene (P3TH/Graphene) composite as the cathode of an aluminum-ion battery. The adjustment of polymer chain spacing by the methyl side chain provides a channel conducive to the transport of large-size AlCl4- complexes. The addition of electron donor groups also changes the electron delocalization characteristics of polymers and improves the specific capacity of the material. At the same time, the in situ composite of graphene can enhance the Π-Π interaction to form a favorable electronic transmission channel. At a current density of 200 mA g-1, the P3TH/Graphene composite showed a specific capacity of ∼150 mA g-1. The flexible structure of the polymer also guarantees the excellent rate capability of the composite.

Asymmetric 1, 2-naphthoquinone cathode material with enhanced capacity for rechargeable aluminium ion batteries

Rechargeable aluminium ion batteries (RAIBs) offer higher safety and lower costs than traditional lithium-ion batteries and have therefore been seen in recent years as a very promising potential development in areas such as large-scale energy storage. However, the development of RAIBs is limited by the cathode material, with most research currently focused on inorganic materials. Organic small molecules like naphthoquinone (NQ) based derivants have the potential to be advantageous in designing high performance cathode materials due to their molecular structural diversity and tunability. Together with 1, 4-NQ, 1, 2-NQ was successfully prepared by chemical oxidation using naphthol derivatives and assembled as RAIBs. Elucidated by Gaussian calculation, the asymmetric structure of 1, 2-NQ provides reaction sites with a higher possibility of binding to AlCl2+ ions than 1, 4-NQ, to the extent that there is an expected enhancement in its electrochemical performance. It is verified by the experimental results that the chemical and electrochemical stability of NQ cathode materials in ionic liquids is improved by the asymmetric structure. The 1, 2-NQ based RAIBs exhibits an outstanding initial specific capacity of 165.9 mAh g−1 and remains at 117.2 mAh g−1 with a Coulombic efficiency of about 98 % after the cycling of 600 and longer cycle life than the 1, 4-NQ based ones. The working concept and satisfying performance of the NQ based cathode material suggest that asymmetric molecules could be a promising design strategy for developing high-performance electrode materials for RAIBs.

Transition metal dichalcogenide-based materials for rechargeable aluminum-ion batteries: A mini-review.

Rechargeable aluminum-ion batteries (AIBs) have emerged as a promising candidate for energy storage applications and have been extensively investigated over the past few years. Due to their high theoretical capacity, nature of abundance, and high safety, AIBs can be considered an alternative to lithium-ion batteries. However, the electrochemical performance of AIBs for large-scale applications is still limited due to the poor selection of cathode materials. Transition metal dichalcogenides (TMDs) have been regarded as appropriate cathode materials for AIBs due to their wide layer spacing, large surface area, and distinct physiochemical characteristics. This mini-review provides a succinct summary of recent research progress on TMD-based cathode materials in non-aqueous AIBs. The latest developments in the benefits of utilizing 3D-printed electrodes for AIBs are also explored.

Manganese–carbon (Mn–C) interaction to host Al3+-ions in a β-MnO2–MWCNT composite cathode in rechargeable aluminium ion batteries

Rechargeable Aluminium Ion Batteries (AIBs) are one of the potential metal battery alternatives to Li-ion batteries.

Development of Iron Fluoride Based Nanocomposite Materials to Enable High Performance Aluminium-Ion Batteries

Developing grid-scale energy storage is important for the penetration of intermittent renewable energies such as wind and solar, but remains one of the biggest challenges in the field of electrochemical energy storage [1]. The application of mature lithium-ion batteries (LIBs) to grid energy storage is controversial due to the limited Li resources and geographical distribution, high cost of materials (e.g., Co, Li), limited lifetime, and safety concerns [2]. Rechargeable aluminium ion batteries (AIBs), which normally utilises aluminium (Al) metal as anode, are one of the most promising battery technologies for future large-scale energy storage, due to the high theoretical volumetric capacity (8046 mAh cm−3), high safety, and low cost and high abundance of aluminium (the third most abundant metal in the earth crust) [3].AIBs have achieved long cycle life (>7500 cycles) when using graphite and graphene as cathode materials [4-5]. Nevertheless, the reported graphite-based cathodes have intrinsically low storage capacities (60–200 mAh g-1) due to the intercalation mechanism of the solvated ions rather than the multivalent Al3+ transformation. Extensive efforts have been made to develop new cathode materials to promote the specific/volumetric capacity of AIBs, including transition metal oxides [6], sulfides [7], selenides [8] and others. These AIBs based on non-graphite cathodes usually demonstrate either low discharge voltage, or high initial capacity but significant capacity decay and poor cycle life. To further improve the performance of AIBs, new cathode materials with high storage capacity and long cycle life needs to be developed.In this paper, we report the development of a nanoscale FeF3@expaned graphite (EG) composite as a novel conversion-type cathode material for AIBs [9]. AIB coin cells were assembled using high-purity Al foil as the anode, the ionic liquid [EMIm]Cl/AlCl3 as the electrolyte, and the FeF3@EG composite as cathode. The conversion reaction between the Al3+ ions and FeF3 through transferring three electrons for per Al3+ ion reacted could boost the storage capacity of AIBs. A single-wall carbon nanotube-modified separator was introduced into the system, to significantly restrict the shuttle effect of the intermediate product of FeF3. The assembled AIBs exhibited a satisfactory reversible specific capacity of 266 mAh g-1 at a current density of 60 mA g-1 after 200 cycles, and a good Coulombic efficiency approaching 100% after 400 cycles at a current density of 100 mA g-1 [9]. Ex-situ X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been applied to explore the energy storage mechanism of FeF3 in AIBs for the first time [9].To further overcome the corrosion issue of ionic liquid, a gel polymer electrolyte (GPE) has been successfully synthesised via an innovative method where no solvent or initiator was utilised in the polymerisation process. The application of GPE significantly reduced the corrosivity and enhances the moisture sensitivity of EMIC ionic liquid, as well as improving the reversible ability of the AIBs. The FeF3@EG-based AIB with 0.8g-EMIC-gel electrolyte exhibits a reversible capacity of 204.5 mAh g-1after 1000 cycles at a current density of 100 mA g-1 and stable rate performance for 600 cycles with a Coulombic efficiency of approximately 95%.This work provides unprecedented insight into novel conversion type cathode materials for AIBs. The findings in this work can serve as guidance for the successful design of low cost and high discharge capacity AIBs for large-scale energy storage and are also meaningful for the fundamental understanding of the metal fluorides cathodes for AIBs.

Ultrahigh Capacity from Complexation-Enabled Aluminum-Ion Batteries with C70 as the Cathode.

Restricted by the available energy storage modes, currently rechargeable aluminum-ion batteries (RABs) can only provide a very limited experimental capacity, regardless of the very high gravimetric capacity of Al (2980mAhg-1 ). Here, a novel complexation mechanism is reported for energy storage in RABs by utilizing 0D fullerene C70 as the cathode. This mechanism enables remarkable discharge voltage (≈1.65V) and especially a record-high reversible specific capacity (750mAhg-1 at 200mAg-1 ) of RABs. By means of in situ Raman monitoring, mass spectrometry, and density functional theory (DFT) calculations, it is found that this elevated capacity is attributed to the direct complexation of one C70 molecule with 23.5 (super)halogen moieties (superhalogen AlCl4 and/or halogen Cl) in average, forming (super)halogenated C70 ·(AlCl4 )m Cln-m complexes. Upon discharging, decomplexation of C70 ·(AlCl4 )m Cln-m releases AlCl4 - /Cl- ions while preserving the intact fullerene cage. This work provides a new route to realize high-capacity and long-life batteries following the complexation mechanism.

Tin oxide quantum dots embedded between graphene sheets to improve non-aqueous aluminum ion battery performance

A composite of tin oxide quantum dots (SnO2QDs) and reduced graphene oxide (RGO), was synthesized using the rapid microwave synthesis method and used as cathode material in the non-aqueous aluminum ion battery. In addition, graphene oxide (GO) and RGO were also prepared separately, and the properties of the resulting cathode materials were compared using XRD, FESEM, Raman, and HRTEM. RGO/SnO2QDs, GO, and RGO were mixed separately with a binder at a ratio of 90:10 and the resulting slurries were coated on a graphite sheet. The electrochemical performance of the graphite sheet, GO, RGO, and RGO/SnO2QDs cathodes was investigated using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge tests in an electrochemical cell containing an ionic liquid (AlCl3/Et3NHCl) as an electrolyte and aluminum as an anode. The battery with RGO/SnO2QDs cathode exhibited an excellent specific discharge capacity of 231 mAh g−1 at 2 A g−1 after 300 cycles with a Coulomb efficiency of 98.3 %. Furthermore, after 25,000 charge and discharge cycles at 2.5 A g−1, the Al||RGO/SnO2QDs battery demonstrated a specific discharge capacity of 163 mAh g−1, with a Coulombic efficiency of 89 %. Additionally, the superior battery also displayed impressive speed performance, achieving a specific discharge capacity of 124.6 mAh g−1 at 4 A g−1, with a Coulombic efficiency of 98.6 %. A comparison of the results of four prepared batteries showed that the synergistic effect of SnO2QDs and RGO layers makes for a suitable cathode material for rechargeable aluminum-ion batteries.

A Bi-based artificial interphase to achieve ultra-long cycling life of Al-metal anode in non-aqueous electrolyte

Rechargeable aluminum-ion batteries (RAB) with Al-metal anode are regarded as cost-effective and environmentally sustainable energy storage systems. However, tapping the high volumetric capacity of the Al-anode has been a challenge because of the spontaneous and irreversible formation of the oxide layer on its surface that renders it electrochemically inactive. Though recently reported AlCl3-based electrolytes overcome this problem by breaking down this oxide layer, their highly corrosive nature hampers commercialization. Here, we investigate a novel approach to protect the Al-anode from severe oxidation by engineering an artificial protective interphase. A unique and less corrosive combination of Al(CF3SO3)3 salt and BiCl3 additive reacts with the Al-anode intrinsically to form an inorganic-rich protective bilayer. This layer is electronically insulating and significantly reduces the charge transfer resistance and surface activation energy at the anode, enabling plating/stripping at extremely low overpotential of <0.1 V that can be sustained for record-long cycling times of >4000 h.

The synergistic effect of Lewis acidic etching V4C3(MXene)@CuSe2/CoSe2 as an advanced cathode material for aluminum batteries

Herein, we focused on the development of the V4C3 MXene composite bimetallic selenide heterostructure (V4C3@CuSe2/CoSe2) as a cathode material for aluminum batteries. This heterostructure was prepared through a Lewis melt salt etching and selenization process. By capitalizing on the synergistic effect between the bimetallic selenide and V4C3 MXene, V4C3@CuSe2/CoSe2 exhibited rapid charge transfer and demonstrated superior discharge specific capacity compared to V4C3 composite monometallic selenide. Furthermore, the incorporation of V4C3 improved the material's stability during charging/discharging. The initial discharge specific capacity of V4C3@CuSe2/CoSe2 reached an impressive 809 mAh g–1 at 1 A g–1. Even after nearly 3000 cycles, it retained a substantial capacity of 169.1 mAh g–1. Ex-situ XPS analysis confirmed the reversible valence transitions of Cu, Co, and Se elements as the main energy storage reactions taking place in the cathode material. Density functional theory analysis provided further insights, revealing that the strong metallic behavior of the heterostructure stemmed from the charge rearrangement facilitated by the bimetallic selenide structure and the optimization of the energy level structure. Additionally, the presence of the bimetallic selenide structure significantly improved the adsorption efficiency of [AlCl4]–. Overall, this research contributes to the advancement of rechargeable aluminum ion batteries and presents a promising avenue for future developments in composite metal selenide structures and MXene-based materials.

Investigating Intercalation of Chloroaluminate Anions in Graphene-Based Materials for Rechargeable Aluminum-Ion Batteries

Development of energy storage systems with high energy and power density, high safety, long cycle life, and low cost is crucial for various applications, including portable electronics and grid storage of renewable energies. Among various battery technologies, rechargeable aluminum ion batteries are particularly attractive due to the abundance, low cost, and safety of aluminum. However, unlike lithium ion batteries, many aspects of the fundamental intercalation processes and dynamics in these aluminum-based battery systems remain unresolved. In this study, we investigate the intercalation of chloroaluminate ions in atomically thin carbon cathodes using mesoscopic devices for charge transport and operando optical microscopy. These measurements provide insights into the energetics and dynamics of intercalation processes in atomically thin samples. We compare the atomically thin single crystal measurements to the cycling response of a high-performance rechargeable aluminum ion battery consisting of a few-layer graphene–multiwall carbon nanotube composite cathode. Our findings show that these nano-composites exhibit a high specific capacity and cyclic stability at high current densities, with a ~3-fold improvement in overall ion diffusivity in the aluminum ion battery. However, the battery cells still exhibit chloroaluminate diffusivities less than ~1% of those in mesoscopic single crystals. Our results highlight the distinction between intrinsic and ensemble electrochemical behavior in aluminum-based batteries and demonstrate that engineering ion transport to enhance diffusivity in these devices can lead to significant improvements in battery performance.

Air-Stable Binary Hydrated Eutectic Electrolytes with Unique Solvation Structure for Rechargeable Aluminum-Ion Batteries

HighlightsA non-corrosive and air-stable hydrated eutectic electrolyte is developed.The electrolyte is composed of aluminum perchlorate nonahydrate and methylurea.The unique solvation structure enables reversible deposition/stripping of Al.The Al-ion battery in this electrolyte shows good charge/discharge performance.

Spatial reticulate polytriphenylamine cathode material with enhanced capacity for rechargeable aluminum ion batteries

Spatial reticulate polytriphenylamine cathode material with enhanced capacity for rechargeable aluminum ion batteries

Lewis Acid-Induced Reversible Disproportionation of TEMPO Enables Aqueous Aluminum Radical Batteries.

Nitroxide radicals, such as 2,2,6,6-tetramethylpiperidyl-1-oxy (TEMPO), are typical organic electrode materials featuring high redox potentials and fast electrochemical kinetics and have been widely used as cathode materials in multivalent metal-ion batteries. However, TEMPO and its derivatives have not been used in emerging rechargeable aluminum-ion batteries (AIBs) due to the known disproportionation and possible degradation of nitroxide radicals in acidic conditions. In this study, the (electro)chemical behavior of TEMPO is examined in organic and aqueous Lewis acid electrolytes. Through in situ (electro)chemical characterizations and theoretical computation, we reveal for the first time an irreversible disproportionation of TEMPO in organic Al(OTf)3 electrolytes that can be steered to a reversible process when switching to an aqueous media. In the latter case, a fast hydrolysis and ligand exchange between [Al(OTf)3TEMPO]- anion and water enable the overall reversible electrochemical redox reaction of TEMPO. These findings lead to the first design of radical polymer aqueous AIBs that are fire-retardant and air-stable, delivering a stable voltage output of 1.25 V and a capacity of 110 mAh g-1 over 800 cycles with 0.028% loss per cycle. This work demonstrates the promise of using nonconjugated organic electroactive materials for cost-effective and safe AIBs that currently rely on conjugated organic molecules.

CMK3 collaborated with SexSy to build high-performance rechargeable aluminum-ion batteries

The development of rechargeable aluminum batteries (RABs) has consistently relied on the logical selection and design of cathode materials. Se has a high electrical conductivity while S has a high theoretical specific capacity; yet, both materials are known to present lethal shuttle effects, space expansion, and slow reaction kinetics. The development of RABs will be accelerated if the synergistic properties of both materials can be utilized. Various ratios of SexSy as the cathode materials for RABs, and a series of electrochemical tests are shown in this work. The rise in the ratio of Se and S leads to the improvement of the cycling performance. However, the shuttle effect of Se and S has a fatal blow to the performance of the battery. To solve this problem, (mesostructured carbon materials) CMK3 modified separators were employed between the cathode and anode to further limit the dissolution of Se, considerably improving the utilization of the active materials. Therefore, initial capacity of Al/GF/C@CMK-3/SexSy is about 539.4 mAh g−1 and reversible capacity of 314.2 mAh g−1 was likewise maintained after 500 cycles at 1.0 A g−1. RABs based on Al/S and Al/Se batteries have promising research avenues opened up by Al/SexSy batteries based on CMK3 modified separators.

Organic Cathode Materials for Rechargeable Aluminum-Ion Batteries.

Organic electrode materials (OEMs) have shown enormous potential in ion batteries because of their varied structural components and adaptable construction. As a brand-new energy-storage device, rechargeable aluminum-ion batteries (RAIBs) have also received a lot of attention due to their high safety and low cost. OEMs are expected to stand out among many traditional RAIB cathode materials. However, how to improve the electrochemical performance of OEMs in RAIBs on a laboratory scale is still challenging. This work reviews and discusses the uses of conductive polymers, carbonyl compounds, imine polymers, polycyclic aromatic hydrocarbons, organic frameworks, and other organic materials as the cathodes of RAIBs, as well as energy-storage mechanisms and research progress. It is hoped that this Review can provide the design guidelines for organic cathode materials with high capacity and great stability used in aluminum-organic batteries and develop more efficient organic energy storage cathodes.

Effects of Multiple Ion Reactions Based on a CoSe2 /MXene Cathode in Aluminum-Ion Batteries.

Rechargeable aluminum-ion batteries (RAIBs) have emerged as a promising battery storage technology owing to their cost-effectiveness, operational safety, and high energy density. However, their actual capacity is substantially lower than their true capacity and their cycling stability is poor. Therefore, understanding the energy-storage mechanism may contribute to the successful design of a stable electrode material, on which the performance can be optimized. The aim of this study is to investigate AlCl4 - ions in transition metal cathode materials and mechanisms that enable for their high-energy-storage potential and low Coulombic efficiency. Results of theoretical analysis and experimental verification show that a multi-ion transport mechanism is responsible for the electrochemical behavior of the battery. The lattice distortion of CoSe2 caused by AlCl4 - ion intercalation, has a considerable effect on the initial stability of the battery. MXene as a support material reduces the size of CoSe2 growing on its surface, effectively inhibiting the lattice distortion caused by the interaction with the aluminum-anion complex, thus addressing the issues of poor reversibility, cycle instability, and low Coulombic efficiency of the battery. Hence, understanding the impact of MXene on the battery may aid in further improving the design of electrode materials.

Organopolysulfides as high-performance cathode materials for rechargeable aluminum-ion batteries

The development of aluminum-ion batteries (AIBs) is significantly confined by the limited high-performance cathode materials. Herein, organopolysulfides are investigated as active cathode materials to fabricate AIBs. A liquid-phase phenyl tetrasulfide (PTS) can deliver a capacity above 600 mAh g−1 after activation, with the maintenance of 253 mAh g−1 after 100 cycles. Owing to the different S locations, PTS shows several voltage plateaus and an average voltage of ∼0.7 V vs. Al3+/Al with no decay upon cycling. More importantly, the liquid PTS can serve as a high-Coulombic-efficiency cathode (∼99.88% ± 0.57% after stabilization), enlighting the design of high-efficiency and low-resistance conversion-type cathode materials for AIBs. By experimental characterizations accompanied by theoretical calculations, it is found that PTS undergoes stepwise reaction procedures during discharge with final products of Al2S3 and AlCl2-coordinated phenyl sulfide, and partially reforms with elemental S and other organopolysulfides during charge. This study demonstrates new opportunities for the design of high-efficiency conversion-type cathode materials for advanced AIBs.

Research Progress of Cathode Materials for Rechargeable Aluminum Batteries in AlCl3/[EMIm]Cl and Other Electrolyte Systems

AbstractThe development of safe, cheap, and environmentally friendly advanced rechargeable batteries with high energy density are one of the most pressing tasks for today‘s energy crisis. With the advantages of low cost, abundant reserves, and high‐level safety, rechargeable aluminum ion batteries are considered ideal candidates for next‐generation energy storage batteries in the context of large‐scale energy applications. Relevant knowledge of energy storage materials and electrolytes, which possess close connection in between, is undeniably crucial for such research, while ironically, most attention is attracted to merely one element alone, especially the energy storage materials involving micro/nanomaterials. In this review, we focus on cathode materials matching with various electrolyte systems for rechargeable aluminum batteries and manage to provide new ideas for the preparation methods of high‐efficiency electrochemical energy storage materials, with future outlooks in this field.

Phytic acid-doped and ammonium hydroxide de-doped polyaniline cathodes for rechargeable aluminum ion battery

Rechargeable aluminum ion battery (RAIB) is a very promising large-scale energy storage scheme attributed by the advantages of aluminum with large theoretical capacity, high energy density, low cost, abundant earth resources and environment friendliness. The selection and preparation of cathode materials are crucial for the electrochemical performance of RAIB. In this study, the specific capacity and cycle life of RAIB were improved by using polyaniline doped with phytic acid and further optimized by ammonium hydroxide de-doping treatment. Phytic acid doping improves the spatial configuration of polyaniline, making the nanostructure more hierarchical and increasing the specific surface area. More importantly, ammonium hydroxide treatment provides more chemical reaction sites while maintaining hierarchic structural morphology of the material. Due to the advantages above, the de-doped polyaniline cathode obtains an initial discharge-specific capacity of the initial cycle is 78.1 mAh g−1 at a high current density of 1 A g−1. After cycling of 2000, the capacity loss is only 16.7%, and an average decay rate of 0.007% per cycle with the Coulomb efficiency remains about 100% after cycling of 5000. At the same time, the contribution of pseudo capacitance and working mechanism are investigated. The capacity contribution of RAIB has been divided into diffusion-control, surface-control and double-layer, which is more consistent with the actual situation and further deepens the understanding of the charging-discharging mechanism of RAIB. These results are expected to lay a foundation for the future development of RAIB systems for large-scale energy storage using organic polymers as cathode materials.

Cover Picture: High Performance and Long‐cycle Life Rechargeable Aluminum Ion Battery: Recent Progress, Perspectives and Challenges (Chem. Rec. 12/2022)

Cover Picture: High Performance and Long‐cycle Life Rechargeable Aluminum Ion Battery: Recent Progress, Perspectives and Challenges (Chem. Rec. 12/2022)