Aluminum-ion Batteries Research Articles

Synergistic Effect of Anodic Hydrophilic and Hydrophobic Interfaces for Long Cycle Life Aqueous Aluminum–Zinc Hybrid Ion Batteries

AbstractAqueous aluminum ion batteries (AAIBs) have drawn considerable attention due to their intrinsic safety, cost‐effectiveness, eco‐friendliness, and high theoretical capacity of aluminum. Currently, suitable anode materials are crucial for the development of high‐performance AAIBs. For the first time, a hydrophilic (ZnCr2O4) and hydrophobic (PVDF) layer modified zinc anode paired with an aluminum‐based aqueous electrolyte to construct a high‐performance aluminum–zinc hybrid ion battery. The Hydrophilic ZnCr2O4 layer of anode endows the battery with low polarization by boosting the pre‐desolvation and deposition kinetics of aluminum/zinc ions. Meanwhile, the hydrophobic PVDF layer suppresses water‐induced corrosion of the anode. The synergistic effect of the hydrophilic and hydrophobic layers of the anode stimulates the battery to exhibit unprecedented cycle life (> 6000 cycles) and considerable discharge capacity (280 mAh g−1), compared to the batteries proposed in previous works paired with aluminum alloy anodes and aluminum‐based aqueous electrolytes. This novel anode provides powerful backing for the development of long‐life and high‐capacity aqueous polyvalent ion batteries due to its low cost and simple fabrication process.

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.

Density Functional Theory Study of Aluminum Ion Batteries Based on AlF4 Clusters Using AIN as Cathode Material

Density Functional Theory Study of Aluminum Ion Batteries Based on AlF₄ Clusters Using AIN as Cathode Material

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

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

Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - ​​Ion Battery

The increasing of need for portable electrical energy makes the demand for rechargeable batteries high. Aluminum-ion battery with Solid Polymer Electrolyte (SPE) produced from the natural polymer corn starch with salt additive has the potential to be developed. The flexibility and resilience of SPE are enhanced by glycerol (C3H8O3). Throughing gelatinization of the linear monomer chains to become amorphous, the space for the ions in it is more free so that the ionic conductivity is high. By means of solution casting, heating temperature of 50°C for 9 hours found SPE with a strong structure. With the same concentration CS-Al has a higher conductivity with σ = 4.93 x 10-5 S/cm than CS-Na whose value is σ = 2,92 x 10-5 S/cm. This is due to the SPE CS-Al show more amorphous structure which allow more flexible ionic segmental motion. This is in accordance with XRD resulting which shows that the addition of aluminum nitrate salt is more amorphous than sodium acetate; the shift in peak pattern is also greater due to cation intercalation Al3+ with corn starch. FTIR is the result found that nitrate fixed by corn starch, indicated a change in the hydroxyl group of corn starch amylopectin. SEM photo of result also showed aluminum nitrate salt ion more easily in overcoming than sodium acetate. The indicate of SPE was more homogeneous because corn starch was already intercalated. They are combined to Al3+ and NO3- ions. With this value it can be an appropriate reference for developing SPE on Aluminum-ion batteries with aluminum nitrate salts have higher performance and environment friendly Keywords: Aluminum-ion battery, Solid Polymer Electrolyte, corn starch, ionic conductivity, and Amorphous

Machine learning assisted prediction in the discharge capacities of novel MXene cathodes for aluminum ion batteries

Conventional experimental methods are widely utilized to discover novel cathode materials for aluminum ion batteries (AIB), but their high price and low-efficiency present extra challenges when dealing with the vast family of MXene materials. In order to vigorously promote the application and development of MXene cathodes in aluminum ion batteries, a new accelerable method to predict the discharge capacities based on machine learning is proposed. Firstly, we establish and train the machine learning models which extract from experimental results of several MXene cathodes (Nb2C, Ti3C2, and V2C) to predict the battery status and initial discharge capacity of mentioned cathodes. Secondly, we refine the models using few Ti2C experimental results to successfully predict the battery status and initial discharge capacity for new Ti2C cathode, which exhibit higher capacity and longer cycle life than Nb2C, Ti3C2 and V2C cathodes. This work provides a new method for predicting electrochemical properties of advanced energy materials beyond MXene materials for aluminum-ion batteries, including but not limited to carbon materials or transition metal oxides.

Benzoquinone-Lubricated Intercalation in Manganese Oxide for High-Capacity and High-Rate Aqueous Aluminum-Ion Battery.

Aqueous aluminum-ion batteries are attractive post-lithium battery technologies for large-scale energy storage in virtue of abundant and low-cost Al metal anode offering ultrahigh capacity via a three-electron redox reaction. However, state-of-the-art cathode materials are of low practical capacity, poor rate capability, and inadequate cycle life, substantially impeding their practical use. Here layered manganese oxide that is pre-intercalated with benzoquinone-coordinated aluminum ions (BQ-AlxMnO2) as a high-performance cathode material of rechargeable aqueous aluminum-ion batteries is reported. The coordination of benzoquinone with aluminum ions not only extends interlayer spacing of layered MnO2 framework but reduces the effective charge of trivalent aluminum ions to diminish their electrostatic interactions, substantially boosting intercalation/deintercalation kinetics of guest aluminum ions and improving structural reversibility and stability. When coupled with Zn50Al50 alloy anode in 2m Al(OTf)3 aqueous electrolyte, the BQ-AlxMnO2 exhibits superior rate capability and cycling stability. At 1Ag-1, the specific capacity of BQ-AlxMnO2 reaches ≈300mAhg-1 and retains ≈90% of the initial value for more than 800 cycles, along with the Coulombic efficiency of as high as ≈99%, outperforming the AlxMnO2 without BQ co-incorporation.

Enhanced Al‐Storage Performance by Electronic Properties Optimization and Structural Customization in MOF‐Derived Heterostructure

AbstractChalcogenide cathodes with multi‐electron transfer characteristics are indispensable to aluminum‐ion batteries (AIBs). Nevertheless, their grievous capacity degradation and sluggish reaction kinetics remain fundamental challenges for the practical application. Herein, a Cu2S/Ni3S2 multiphase structure within the metal‐organic frame (MOF) derived carbon decoration layer (CNS@MC) is constructed to elevate the intrinsic electronic properties of chalcogenide cathode and realize high‐performance AIBs. The existence of outer carbon layer and strong orbital interaction at inner heterointerfaces eliminates the bandgap and arises more electrons at Fermi level, efficiently reducing the energy barrier for electron transfer and achieving high reactivity within cathodes. The CNS@MC also presents a strong electronic interaction with active solvent groups, which is beneficial to capture Al3+ and facilitate the three‐electron charge‐storage reactions. Experimental results demonstrate that the tailored CNS@MC cathode possesses superior redox kinetics due to the sufficient surface area and rapid Al‐ion diffusion during cycling. Meanwhile, the robust CNS@MC delivers ultra‐high electrochemical stability (131.1 mAh g−1 over 3500 cycles) with high coulombic efficiency and outstanding rate performance. This work offers new opportunities for optimizing the intrinsic properties of the chalcogenide electrodes based on MOF derivatives and heterostructure, providing novel thoughts for designing high‐performance AIBs.

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.

Engineering High Voltage Aqueous Aluminum-Ion Batteries.

The energy transition to renewables necessitates innovative storage solutions beyond the capacities of lithium-ion batteries. Aluminum-ion batteries (AIBs), particularly their aqueous variants (AAIBs), have emerged as potential successors due to their abundant resources, electrochemical advantages, and eco-friendliness. However, they grapple with achieving their theoretical voltage potential, often yielding less than expected. This perspective article provides a comprehensive examination of the voltage challenges faced by AAIBs, attributing gaps to factors such as the aluminum reduction potential, hydrogen evolution reaction, and aluminum's inherent passivation. Through a critical exploration of methodologies, strategies, such as underpotential deposition, alloying, interface enhancements, tailored electrolyte compositions, and advanced cathode design, are proposed. This piece seeks to guide researchers in harnessing the full potential of AAIBs in the global energy storage landscape.

Revealing the Dominance of the Dissolution-Deposition Mechanism in Aqueous Zn-MnO2 Batteries.

Zn-MnO2 batteries have attracted extensive attention for grid-scale energy storage applications, however, the energy storage chemistry of MnO2 in mild acidic aqueous electrolytes remains elusive and controversial. Using α-MnO2 as a case study, we developed a methodology by coupling conventional coin batteries with customized beaker batteries to pinpoint the operating mechanism of Zn-MnO2 batteries. This approach visually simulates the operating state of batteries in different scenarios and allows for a comprehensive study of the operating mechanism of aqueous Zn-MnO2 batteries under mild acidic conditions. It is validated that the electrochemical performance can be modulated by controlling the addition of Mn2+ to the electrolyte. The method is utilized to systematically eliminate the possibility of Zn2+ and/or H+ intercalation/de-intercalation reactions, thereby confirming the dominance of the MnO2 /Mn2+ dissolution-deposition mechanism. By combining a series of phase and spectroscopic characterizations, the compositional, morphological and structural evolution of electrodes and electrolytes during battery cycling is probed, elucidating the intrinsic battery chemistry of MnO2 in mild acid electrolytes. Such a methodology developed can be extended to other energy storage systems, providing a universal approach to accurately identify the reaction mechanism of aqueous aluminum-ion batteries as well.

Metal Aluminum-Free Configuration Toward High-Performance Aqueous Aluminum Ion Battery

Rechargeable aluminum batteries hold great promise for high energy density and low-cost energy storage applications but are stalled by severe electrochemical side reactions (e.g., dendrite, passivation, and corrosion) at aluminum (Al) metal anode. Here, we design an aluminum ion battery with an Al-free configuration to circumvent the problems caused by the above side reactions. The feasibility of Al x MnO 2 · n H 2 O cathode in aluminum ion batteries is revealed in conjunction with TiO 2 anodes by using the optimal 5 M Al(OTF) 3 electrolyte. The as-assembled aluminum ion battery enables high initial discharge capacity of 370.4 mAh g –1 at 30 mA g –1 , favorable stability with low irreversible capacity loss, and enhanced safety. Further, the mechanism is intensively elucidated by multiple characterization results, indicative of the Al 3+ ions (de)intercalation redox chemistry. Revealed by empirical analyses, the capacity contribution of high-voltage plateau, corresponding to the disproportionation reaction of Mn 3+ in an Al x MnO 2 · n H 2 O battery system, tends to increase with the increasing electrolyte concentration. Our findings may provide fresh impetus to the rational design of aluminum ion batteries with excellent electrochemical properties.

Progress of Advanced Cathode Materials of Rechargeable Aluminum-Ion Batteries

Given the increasing attention to the safety issues of lithium-ion batteries (LIBs) and the continuous rise in the price of lithium and its compounds, it is urgent to explore innovative electrochemical energy device alternatives to LIBs. Major efforts have been devoted to developing rechargeable aluminum-ion batteries (AIBs), owing to their low cost and high energy density derived from the 3-electron redox reaction. Moreover, the dendrite-free plating behavior with room-temperature ionic liquid electrolytes endows AIBs with great safety expectations. A marked hurdle persists in the quest for appropriate cathode materials that can effectively accommodate aluminum ion species in AIBs. This review aims to deliver an integrated overview of the state-of-the-art cathode materials for nonaqueous and aqueous AIBs, with a special emphasis on their underlying electrochemical interaction with electrolytes. The strategies adopted to improve the specific capacity and cyclic performances of AIBs are highlighted. Furthermore, future perspectives of AIBs are discussed.

Expanded graphite with boron-doping for cathode materials of high-capacity and stable aluminum ion batteries.

Recently, aluminum ion batteries (AIBs) have attracted more attention due to the reliable, cost-effective, and air-stable Al metal anode. Among various cathode materials of AIBs, graphite was paid more attention owing to its high-voltage plateau and stable properties in storing chloroaluminate anions (AlCl4 -). However, its low capacity limits the real application and can not satisfy the requirements of modern society. To solve the above issue, herein, boron (B)-doping expanded graphite (B-EG) was prepared by thermal treatment of expanded graphite and boric acid together in a reduction atmosphere. Based on the structural and electrochemical characterization, the results show that B-doping amplifies the interlayer space of expanded graphite (EG), introduces more mesoporous structures, and induces electron deficiency, which is beneficial to accelerating the transfer and adsorption of active ions. The results indicate that the B-EG electrode exhibits excellent rate capability and a high specific capacity of 84.9 mA h g-1 at 500 mA g-1. Compared with the EG electrode, B-EG shows better cycle stability with the specific capacity of 87.7 mA h g-1 after 300 cycles, which could be attributed to lower pulverization and higher pseudo-capacitance contribution of B-EG after the introduction of B species.

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.

Aluminum intercalation behaviours of {[Fe(Tp)(CN)3]2[M(H2O)2]} cyanido-bridged chain compounds in an ionic liquid electrolyte.

As the development of aluminum-ion batteries is still in its infancy, researchers are still dedicated to exploring suitable host materials and investigating their aluminum intercalation behaviours. Here, a series of cyanido-bridged chain compounds with the formula {[FeIII(Tp)(CN)3]2[MII(H2O)2]}n (M = Ni, Co, Mn, Zn, Cu) are studied as cathode electrodes for aluminum-ion batteries with [EMIm]Cl-AlCl3 (1-ethyl-3-methylimidazolium chloride-AlCl3) ionic liquid as the electrolyte. The electrochemical properties suggested Fe3+/Fe2+ to be the redox-active couple during the aluminum intercalation and deintercalation processes of these compounds, and the observed maximum specific capacity obtained by the Fe-Co compound is 200 mA h g-1 despite the rapid specific capacity fading. To gain a deeper understanding of the capacity decay suffered by these compounds, further investigation was conducted to explore the evolution of compounds during the electrochemical measurements. It has been attributed to the following reasons: 1. thermodynamic instability results in the transformation/damage of two of the chain structures (for the Fe-Ni and Fe-Co compounds) during heat treatment on electrodes, a crucial step in electrode preparation; 2. the acidic nature of the electrolyte triggers the destruction of the chain structure, with the appearance of partial reduction of Fe3+ to Fe2+, and a new interaction of the cyano group with aluminum; 3. the high charge density of inserted Al ions makes the chain structure suffer from structural damage during both the charging and discharging processes. The progressive accumulation of trapped intercalated ions hampers their involvement in the reaction, consequently decreasing electrochemical reversibility.

An artificial aluminum-tin alloy layer on aluminum metal anodes for ultra-stable rechargeable aluminum-ion batteries.

Rechargeable aluminum ion batteries (RAIBs) exhibit great potential for next-generation energy storage systems owing to the abundant resources, high theoretical volumetric capacity and light weight of the Al metal anode. However, the development of RAIBs based on Al metal anodes faces challenges such as dendrite formation, self-corrosion, and volume expansion at the anode/electrolyte interface, which needs the rational design of an aluminum anode for high-performance RAIBs. This work proposes a novel and low-cost strategy by utilizing an alloy electrodeposition method in a low-temperature molten salt system to fabricate an aluminum-tin (AlSn) alloy coating layer on copper foil as the anode for RAIBs, which successfully addresses the issues of dendrite formation and corrosion at the anode/electrolyte interface. The artificial AlSn alloy layer could enhance the active sites for metal Al homogeneous deposition and effectively retard the dendrite formation, which was verified by an in situ optical microscopy study. The symmetric AlSn@Cu cell demonstrates a low average overpotential of ∼38 mV at a current density of 0.5 mA cm-2 and a long-term lifespan of over 1100 h. Moreover, the AlSn@Cu//Mo6S8 full cells deliver a high capacity of 114.9 mA h g-1 at a current density of 100 mA g-1 and maintain ultra-stable cycling stability even over 1400 cycles with a ∼100% coulombic efficiency (CE) during the long-term charge/discharge processes. This facile alloy electrodeposition approach for designing high-performance Al-based anodes provides insights into the understanding of artificial interface chemistry on Al-based anodes and potentially accelerates the design of high-performance RAIBs.

SnS2 quantum dots-coated VO2@carbon nanorods for secondary battery displaying high capacity and rate-performance.

Electrode materials optimization is one of the keys to improving the energy storage characteristics of secondary batteries. Herein, a VO2@carbon@SnS2 composite is developed by coating SnS2 quantum dots (QDs) on lamellar VO2@carbon nanorods, yielding a high-performance aluminum-ion battery cathode. SnS2 QDs embedded in VO2@carbon accelerate electron transport, while the in situ coating of carbon improves cycling stability. When cycling at 0.5 A g-1, capacity is maintained at 157.6 mA h g-1 after 200 cycles. Even at 1.0 A g-1, the cathode can be stably cycled 1000 times. Capacity remains at 176.3 mA h g-1 and coulombic efficiency is 99.1% at temperatures below -10 °C after 100 cycles. These findings provide new ideas for the development of QD-modified composites for application in secondary batteries.

Copper tetrathiovanadate (Cu3VS4): a newly emerging electrode for rechargeable aqueous aluminum-ion batteries.

We report the electrochemistry of Al3+ ion storage in copper tetrathiovanadate (Cu3VS4) in an aqueous electrolyte for the first time. It is found that Cu3VS4 could deliver an initial discharge capacity of 111 mA h g-1 at a current rate of 0.5 A g-1 and 77 mA h g-1 up to the 300th cycle at 2 A g-1 along with an excellent rate capability. The better electrochemical performance may be attributed to the high theoretical capacity of sulfur and the superior conductivity of copper which allows facile Al3+ ion diffusion in Cu3VS4. The electrochemical mechanism of Al3+ ion storage is also illustrated.

CuS loaded on reduced graphene oxide prepared by ball milling method as cathode material for high- power aqueous Cu-Al hybrid-ion batteries

Aqueous hybrid-ion batteries (AHBs) are a potential low-cost, high safety, high operating voltage and high energy density storage devices. A new type of AHBs was proposed. We use a simple, low-cost and energy-saving ball milling method for the synthesis of material that CuS anchored on reduced graphene oxide (CuS@rGO). Aqueous Cu-Al hybrid-ion batteries were prepared with CuS@rGO as cathode, Cu as anode and LiCuAl (LiCl, CuCl and AlCl3) aqueous solution as electrolyte. The battery produces a reversible capacity of 218.9 mAh g−1 at 2 A g−1. At a high current density of 5 A g−1, the capacity can also reach 166.7 mAh g−1 and the battery capacity retention rate is as high as 80 % after 500 cycles. The successfully prepared CuS@rGO has excellent rate capability and strong cycling stability at high current density, which exceeds most reported aqueous and nonaqueous systems of Aluminum-ion batteries. The introduction of reduced graphene oxide (rGO) can accelerate the electron transfer in composites and provide better electrochemical kinetics, so it is conducive to the rapid storage of aluminum ions.