An interface-reconstruction effect for rechargeable aluminum battery in ionic liquid electrolyte to enhance cycling performances

Aluminum(Al) metal has been regarded as a promising anode for rechargeable batteries because of its natural abundance and high theoretical specific capacity. However, rechargeable aluminum batteries(RABs) using A1 metal as anode display poor cycling performances owing to interface problems between anode and electrolyte. The solid-electrolyte interphase(SEI) layer on the anode has been confirmed to be essential for improving cycling performances of rechargeable batteries. Therefore, we immerse the Al metal in ionic liquid electrolyte for some time before it is used as anode to remove the passive film and expose fresh Al to the electrolyte. Then the reactions of exposed Al, acid, oxygen and water in electrolyte are occurred to form an SEI layer in the cycle. Al/electrolyte/V_2 O_5 full batteries with the thin, uniform and stable SEI layer on Al metal anode perform high discharge capacity and coulombic efficiency(CE). This work illustrates that an SEI layer is formed on Al metal anode in the cycle using a simple and effective pretreatment process and results in superior cycling performances for RABs.

Bi-salt electrolyte for aqueous rechargeable aluminum battery

The exertion of superior high-energy density based on multivalent ions transfer of rechargeable aluminum batteries is greatly hindered by limited electrochemical stability window of typical water in salt electrolyte(Wi SE). Recently, it is reported that a second salt addition to the Wi SE can offer further suppression of water activities, and achieves a much wider electrochemical window compared with aqueous Wi SE electrolytes. Hence, we demonstrate a class of water in bi-salt electrolyte containing the trifluoromethanesulfonate(OTF), which exhibits an ultra-wide electrochemical window of 4.35 V and a very low overpotential of 14.6 m V. Moreover, the interface chemistry between cathode and electrolyte is also confirmed via kinetic analysis. Surprisingly, we find the electrolyte can effectively suppress Mn dissolution from the cathode, alleviate self-discharge behavior, and ensure a stable electrode–electrolyte interface based on the interface concentrated-confinement effect. Owing to these unique merits of water in bi-salt electrolyte, the AlxMnO_(2)·nH_(2)O material delivers a high capacity of 364 m Ah g;and superb long-term cycling performance > 150 cycles with a capacity decay rate of 0.37% per cycle with coulombic efficiency at ca. 95%.

Emerging rechargeable aqueous aluminum ion battery:Status,challenges,and outlooks

Aluminum ion battery(AIB)technology is an exciting alternative for post-lithium energy storage.AIBs based on ionic liquids have enabled advances in both cathode material development and fundamental understanding on mechanisms.Recently,unlocking chemistry in rechargeable aqueous aluminum ion battery(AAIB)provides impressive prospects in terms of kinetics,cost,safety considerations,and ease of operation.To review the progress on AAIB,we discuss the critical issues on aluminum electrochemistry in aqueous system,cathode material design to overcome the drawbacks by multivalent aluminum ions,and challenges on electrolyte design,aluminum stripping/plating,solid-electrolyte interface(SEI)formation,and design of cathode materials.This review aims to stimulate exploration of high-performance AAIB and rationalize feasibility grounded on underlying reaction mechanisms.

Comments on “An ultrafast rechargeable aluminum ion battery”

Nature published an article'An ultrafast rechargeable aluminum ion battery'On April 6,2015.The authors used many new materials to compose the cell,such as three-dimensional graphitic-foam as the cathode,an ionic liquid electrolyte.The experimental cell has shown well-defined discharge voltage plateaus near 2 V.The cell is mechanically bendable and foldable without affecting its operation.

CoSnO_(3)/C nanocubes with oxygen vacancy as high-capacity cathode materials for rechargeable aluminum batteries

Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-electrons reaction mechanism.However,the development of RABs is greatly limited,because of the lack of advanced cathode materials,and their complicated and unclear reaction mechanisms.Exploring the novel nanostructured transition metal and carbon composites is an effective route for obtaining ideal cathode materials.In this work,we synthesize porous CoSnO_(3)/C nanocubes with oxygen vacancies for utilizing as cathodes in RABs for the first time.The intrinsic structure stability of the mixed metal cations and carbon coating can improve the cycling performance of cathodes by regulating the internal strains of the electrodes during volume expansion.The nanocubes with porous structures contribute to fast mass transportation which improves the rate capability.In addition to this,abundant oxygen vacancies promote the adsorption affinity of cathodes,which improves storage capacity.As a result,the CoSnO_(3)/C cathodes display an excellent reversible capacity of 292.1 mAh g^(-1) at 0.1 A g^(-1),a good rate performance with 109 mAh g^(-1) that is maintained even at 1 A g^(-1) and the provided stable cycling behavior for 500 cycles.Besides,a mechanism of intercalation of Al^(3+)within CoSnO_(3)/C cathode is proposed for the electrochemical process.Overall,this work provides a step toward the development of advanced cathode materials for RABs by engineering novel nanostructured mixed transition-metal oxides with carbon composite and proposes novel insights into chemistry for RABs.

MOF-based quasi-solid-state electrolyte for long-life Al-Se battery

Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and low cycle life due to the shuttle effect.To mitigate the shuttle effect induced by soluble selenium chloroaluminate compound that tends to migrate towards the negative electrode,a quasi-solid-state Al-Se battery was fabricated through the synthesis of a multi-aperture structure quasisolid-state electrolyte(MOF@GPE)based on metal-organic framework(MOF)material and gel-polymer electrolyte(GPE).The high ionic conductivity(1.13×10^(-3)S cm^(-1))of MOF@GPE at room temperature,coupled with its wide electrochemical stability window(2.45 V),can facilitate ion transport kinetics and enhance the electrochemical performance of Al-Se batteries.The MOF@GPE-based quasi-solidstate Al-Se batteries exhibit outstanding long-life cycling stability,delivering a high specific discharge capacity of 548 mA h g^(-1)with a maintained discharge specific capacity of 345 mA h g^(-1)after 500 cycles at a current density of 200 mA g^(-1).The stable ion transmission and high ion transport kinetics in MOF@GPE can be attributed to the stable structure and permeable channel of MOF,which effectively captures the soluble selenium chloroaluminate compound and further restrains the shuttle effect,resulting in improved cycling performance.

Self-supporting and dual-active 3D Co-S nanosheets constructed by ligand replacement reaction from MOF for rechargeable Al battery

Metal sulfides with high theoretical capacities are expected as promising cathode materials of Al batteries(AIBs). However, powdery active materials are mainly synthesized and loaded on current collector by insulating binder without capacity. Meanwhile, S as inert element in metal sulfides can not usually provide capacity. So, powdery metal sulfides only exhibit limiting practical capacity and poor cycling stability due to weak conductivity and low mass utilization. Herein, the novel self-supporting and dual-active Co-S nanosheets on carbon cloth (i.e. Co-S/CC) with hierarchically porous structure are constructed as cathode of AIBs. Co-S nanosheets are derived from ZIF-67 nanosheets on CC by a facile ligand replacement reaction. As a result, the binder-free Co-S/CC cathode with good conductivity delivers excellent initial discharge capacity of 383.4 m Ah g^(-1)(0.211 m Ah cm^(-2)) at current density of 200 m A g^(-1)and maintain reversible capacity of 156.9 m Ah g^(-1)(0.086 m Ah cm^(-2)) with Coulombic efficiency of 95.8% after 500 cycles,which are much higher than those of the traditional slurry-coating cathodes. Both Co and S as active elements in Co-S/CC contribute to capacity, which leads to a high mass utilization. This work provides a significant strategy for the construction of self-supporting metallic cathode for advanced high-energy density Al battery.

Reversible Al^(3+) storage mechanism in anatase TiO_(2) cathode material for ionic liquid electrolyte-based aluminum-ion batteries

Rechargeable aluminum ion battery(AIB) with high theoretical specific capacity, abundant elements and low cost engages considerable attention as a promising next generation energy storage and conversion system. Nevertheless, to date, one of the major barriers to pursuit better AIB is the limited applicable cathode materials with the ability to store aluminum highly reversibly. Herein, a highly reversible AIB is proposed using mesoporous TiO2 microparticles(M-TiO2) as the cathode material. The improved performance of Ti O2/Al battery is ascribed to the high ionic conductivity and material stability, which is caused by the stable architecture with a mesoporous microstructure and no random aggregation of secondary particles. In addition, we conducted detailed characterization to gain deeper understanding of the Al^(3+) storage mechanism in anatase Ti O2 for AIB. Our findings demonstrate clearly that Al^(3+)can be reversibly stored in anatase TiO2 by intercalation reactions based on ionic liquid electrolyte. Especially, DFT calculations were used to investigate the accurate insertion sites of aluminum ions in M-Ti O2 and the volume changes of M-TiO2 cells during discharging. As for the controversial side reactions in AIBs, in this work, by normalized calculation, we confirm that M-Ti O2 alone participate in the redox reaction. Moreover, cyclic voltammetry(CV) test was performed to investigate the pseudocapacitive behavior.

Nanoconfinement effect of nanoporous carbon electrodes for ionic liquid-based aluminum metal anode

Rechargeable aluminum batteries(RABs),which use earth-abundant and high-volumetric-capacity metal anodes(8040 m Ah cm-3),have great potential as next-generation power sources because they use cheaper resources to deliver higher energies,compared to current lithium ion batteries.However,the mechanism of charge delivery in the newly developed,ionic liquid-based electrolytic system for RABs differs from that in conventional organic electrolytes.Thus,targeted research efforts are required to address the large overpotentials and cycling decay encountered in the ionic liquid-based electrolytic system.In this study,a nanoporous carbon(NPC)electrode with well-developed nanopores is used to develop a high-performance aluminum anode.The negatively charged nanopores can provide quenched dynamics of electrolyte molecules in the aluminum deposition process,resulting in an increased collision rate.The fast chemical equilibrium of anionic species induced by the facilitated anionic collisions leads to more favorable reduction reactions that form aluminum metals.The nanoconfinement effect causes separated nucleation and growth of aluminum nanoparticles in the multiple confined nanopores,leading to higher coulombic efficiencies and more stable cycling performance compared with macroporous carbon black and 2D stainless steel electrodes.

Sulfur-linked carbonyl polymer as a robust organic cathode for rapid and durable aluminum batteries

Rechargeable aluminum batteries are believed as a promising next-generation energy-storage system due to abundant low-cost Al sources and high volumetric specific capacity.The Al-storage cathodes,however,are plagued by strong electrostatic interaction between host materials and carrier ions,leading to large overpotential and undesired cycling stability as well as sluggish ion diffusion kinetics.Herein,sulfur-linked carbonyl polymer based on perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA) as the cathode materials for ABs is proposed,which demonstrates a small voltage polarization(135 mV),a reversible capacity of 110 mAh g^(-1) at 100 mA g^(-1) even after 1200 cycles,and rapid Al-storage kinetics.Compared with PTCDA,the sulfide polymer possesses higher working voltage because of its lower LUMO energy level according to theoretical calculation.The ordered carbonyl active sites in sulfide polymer contribute to the maximized material utilization and rapid ion coordination and dissociation,resulting in superior rate capability.Besides,the bridged thioether bonds endow the polysulfide with robust and flexible structure,which inhibits the dissolution of active materials and improves cycling stability.This work implies the importance of ordered arrangement of redox active moieties for organic electrode,which provides the theoretical direction for the structural design of organic materials applied in multivalent-ion batteries.

Non-stoichiometric CoS_(1.097) nanoparticles prepared from CoAl-layered double hydroxide and MOF template as cathode materials for aluminum-ion batteries

As a main force in the energy evolution,lithium-ion batteries(LIBs)have been extensively studied in recent decades and are widely used in energy storage and portable electronic products as a result of their advantages of high working voltage and long cycle performance.

Isolated Co single atoms in nitrogen-doped graphene for aluminum-sulfur batteries with enhanced kinetic response

Al-S batteries are promising next generation energy storage devices due to their high theoretical energy density(1340 Wh kg^(-1)),low cost,and safe operation.However,the electrochemical performance of Al-S batteries suffers poor reversibility owing to slow kinetic processes determined by the difficulty of reversible conversion between Al and S.Here,we proposed a single-atom catalysts comprising Co atoms embedded in a nitrogen-doped graphene(Co NG)as an electrochemical catalyst in the sulfur cathode that renders a reduced discharge-charge voltage hysteresis and improved sulfur utilization in the cathode.The structural and electrochemical analyses suggest that the Co NG facilitated both the formation and oxidation of Al S;during the electrochemical reactions of the sulfur species.Consequently,the Co NG-S composite can deliver a considerably reduced voltage hysteresis of 0.76 V and a reversible specific capacity of 1631 m Ah g^(-1) at 0.2 A g^(-1) with a sulfur utilization of more than 97%.

Electrochemically triggered decoupled transport behaviors in intercalated graphite:From energy storage to enhanced electromagnetic applications

Pyrolytic graphite (PG) with highly aligned graphene layers,present anisotropic electrical and thermal transport behavior,which is attractive in electronic,electrocatalyst and energy storage.Such pristine PG could meeting the limit of electrical conductivity (~2.5×10^(4) S·cm^(−1)),although efforts have been made for achieving high-purity sp^(2) hybridized carbon.For manipulating the electrical conductivity of PG,a facile and efficient electrochemical strategy is demonstrated to enhance electrical transport ability via reversible intercalation/de-intercalation of AlCl_(4)^(-)into the graphitic interlayers.With the stage evolution at different voltages,variable electrical and thermal transport behaviors could be achieved via controlling AlCl_(4)^(-)concentrations in the PG because of substantial variation in the electronic density of states.Such evolution leads to decoupled electrical and thermal transport (opposite variation trend) in the in-plane and out-of-plane directions,and the in-plane electrical conductivity of the pristine PG (1.25×10^(4) S·cm^(−1)) could be massively promoted to 4.09×10^(4) S·cm(AlCl_(4)^(-)intercalated PG),much better than the pristine bulk graphitic papers used for the electrical transport and electromagnetic shielding.The fundamental mechanism of decoupled transport feature and electrochemical strategy here could be extended into other anisotropic conductive bulks for achieving unusual behaviors.

Surficial modification enabling planar Al growth toward dendrite-free metal anodes for rechargeable aluminum batteries

Al metal possesses ultrahigh theoretical volumetric capacity of 8,040 m Ah cm^(-3),and gravimetric capacity of 2,980 m Ah g^(-1),and thus is highly attractive for electrochemical energy storage.However,it suffers from several issues,such as the dendrite formation,during Al stripping-deposition cycling,which has been verified to account for the short circuit and limited cyclic performance.Herein,we use a facile and applicable method to in-situ reconstruct the Al anode surface with F-Al-O chemical bonds,which could preferentially induce the planar growth of Al along the interface plane,thus leading to the dendrite-free morphology evolution during the cycling.Benefiting from F-Al-O chemical bonds on the surface of Al anodes,long lifespan of symmetric cells can be realized even under 1 m A cm^(-2)and 1 m Ah cm^(-2).Coupling the F-Al anode with graphite-based cathodes,high-voltage dual-ion Al metal batteries can be achieved with long-term cycle stability up to 1,200 cycles(at 0.5 m A cm^(-2)),surpassing the counterparts using pristine Al metal anode.Furthermore,the effectiveness of this surficial modification strategy is also elucidated with the aid of theoretical calculation.This work provides novel insights on low-cost and facile strategies against the Al dendrite growth in aluminum batteries.

Multi-electron reaction and fast Al ion diffusion of δ-MnO_(2) cathode materials in rechargeable aluminum batteries via first-principle calculations

Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO_(2) are not clear. Hence, based on the first-principles calculations, key influencing factors of slow Al-ions diffusion are narrow pathways, unstable Al-O bonds and Mn^(3+) type polaron have been identified by investigating four types of δ-MnO_(2)(O3, O'3, P2 and T1). Although Al insert into δ-MnO_(2) leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO_(2) keeps the long(spacious pathways)and stable(2.007–2.030 A) Al-O bonds resulting in the lower energy barrier of Al diffusion of 0.56 e V. By eliminated the influence of Mn^(3+)(low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 e V in P2 type, confirming the obviously effect of Mn^(3+) polaron. On the contrary, although the T1 type MnO_(2) has the sluggish of Al-ions diffusion, the larger interlayer spacing of Mn-Mn layer,causing by H_(2)O could assist Al-ions diffusion. Furthermore, it is worth to notice that the multilayer δ-MnO_(2) achieves multi-electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2(1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO_(2) should keep more P2-type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage.

Modified Al negative electrode for stable high-capacity Al-Te batteries

Metal aluminum batteries(MABs)are considered potential large-scale energy storage devices because of their high energy density,resource abundance,low cost,safety,and environmental friendliness.Given their high electrical conductivity,high theoretical specific capacity,and high discharge potential,Te is considered a potential positive electrode material for MABs.Nonetheless,the critical issues induced by the chemical and electrochemical dissolution of tellurium and subsequent chemical precipitation on bare Al negative electrodes result in poor cycle stability and low discharge capacity of Al-Te batteries.Here an efficient TiB_(2)-based modified layer has been proposed to address bare Al electrodes(Al/TB).Consequently,the low-voltage hysteresis and long cycle life of the Al/TB negative electrode have been achieved.In addition,the electrochemical performance of the Al-Te battery based on the Al/TB negative electrode is dramatically improved.Furthermore,the modified separator technology is introduced to match with the as-designed Al/TB negative electrode.Therefore,the record-setting long-term cycle stability of up to 500 cycles has been achieved in the Al-Te battery.The facile strategy also opens a potential route for other high-energy density battery systems,such as Al-S and Al-Se batteries.

Rechargeable metal(Li, Na, Mg, Al)-sulfur batteries: Materials and advances

Energy and environmental issues are becoming more and more severe and renewable energy storage technologies are vital to solve the problem.Rechargeable metal(Li,Na,Mg,Al)-sulfur batteries with low-cost and earth-abundant elemental sulfur as the cathode are attracting more and more interest for electrical energy storage in recent years.Lithium-sulfur(Li-S),room-temperature sodium-sulfur(RT Na-S),magnesium-sulfur(Mg-S)and aluminum-sulfur(Al-S)batteries are the most prominent candidates among them.Many obvious obstacles are hampering the developments of metal-sulfur batteries.Li-S and Na-S batteries are encumbered mainly by anode dendrite issues,polysulfides shuttle and low conductivity of cathodes.Mg-S and Al-S batteries are short of suitable electrolytes.In this review,relationships between various employed nanostructured materials and electrochemical performances of metal-sulfur batteries have been demonstrated.Moreover,the selections of suitable electrolytes,anode protection,separator modifications and prototype innovations are all crucial to the developments of metal-sulfur batteries and are discussed at the same time.Herein,we give a review on the advances of Li-S,RT Na-S,Mg-S and Al-S batteries from the point of view of materials,and then focus on perspectives of their future developments.

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

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

Realizing the Long Lifespan of Molybdenum Trioxide in Aqueous Aluminum Ion Batteries Through Potential Regulation

MoO_(3) is one of the most promising anode materials for aqueous aluminum batteries due to its high theoretical capacity and suitable aluminum insertion/de-insertion potential.However,the inferior cycling stability limits its further application,and the failure mechanism is still unclear.In this article,we provide a straightforward potential regulation technique to manage phase evolution during the charge/discharge process,which ultimately results in a markedly enhanced MoO_(3) electrode cycling stability.The failure mechanism study reveals that the excessive oxidation of the electrode during charge/discharge generates the H_(0.34)MoO_(3) phase,which has high solubility and is the primary cause of MoO_(3) deactivation.Although the dissolved Mo species will be deposited onto the electrode sheet again,the deposition is not electrochemically active and cannot contribute to the capacitance.Controlling the cutoff potential prevented the production of H_(0.34)MoO_(3),resulting in excellent cycling performance(80.1% capacity retention after 4000 cycles).The as-assembled α-MoO_(3)//MnO_(2) full battery exhibits high discharge plateaus(1.4 and 0.9 V),large specific capacity(200 mAhg^(-1) at 2 Ag^(-1)),and ultra-high coulombic efficiency(99%).The research presented here may contribute to the development of highly stable electrode materials for aqueous batteries.

Charge storage mechanisms of cathode materials in rechargeable aluminum batteries

Rechargeable aluminum batteries(RABs)have attracted great interest as one of the most promising candidates for large-scale energy storage because of their high volumetric capacity,low cost,high safety and the abundance of aluminum.However,compared with the aluminum anodes,the cathode materials face more problems including low specific capacity,relatively sluggish kinetics in most host structures and/or limited cycle lifespan,which pose the major challenge for RABs in further practical applications.During the past years,intensive efforts have been devoted to developing new cathode materials and/or designing engineered nanostructures to greatly improve RABs’electrochemical performances.In addition to nanotechnologybased electrode structure designs,the intrinsic chemical structures and charge storage mechanisms of cathode materials play an equally crucial role,if not more,in revolutionizing the battery performances.This review,here,focuses on current understandings into the charge storage mechanisms of cathode materials in RABs from a chemical reaction point of view.First,the fundamental chemistry,charge storage mechanisms and design principles of RAB cathode materials are highlighted.Based on different ion charge carriers,the current cathode materials are classified into four groups,including Al^(3+)-hosting,Al Cl_(4)^(-)-hosting,Al Cl_(2)^(+)/Al Cl_(2)^(+)-hosting,and Cl^(-)-hosting cathode materials.Next,the respective typical electrode structures,optimization strategies,electrochemical performances and charge storage mechanisms are discussed in detail to establish their chemistry-structure-property relationships.This review on current understandings of the cathode charge storage mechanisms will lay the ground and hopefully set new directions into the rational design of high-performance cathode materials in RABs,and open up new opportunities for designing new electrolyte systems with respect to the targeted cathode systems.