Hybrid Ion Battery Research Articles

High-Power and Long-Lifespan Rechargeable Ion Batteries based on Na+-Confined Na+/Mg2+ Coinsertion Chemistry.

Magnesium-sodium hybrid ion batteries (MSHIBs) are expected to achieve excellent rate capability. However, existing MSHIB cathodes exhibit low ionic conductivity and poor structural stability, resulting in low power density and cycle lifespan. Herein, sodium-rich Na3.7V6O16·2.9H2O (Na-rich NVO) nanobelts are synthesized as MSHIB cathodes. Excess Na+ induced NaO5 and NaO3 interlayer pins, which ensures NVO structural stability to accommodate Mg2+ and Na+. They also confine the migration pathway of cations to the diffusion direction, lowering the migration barriers of Mg2+ and enhancing the ionic conductivity. Excess interlayer Na+ increases the electronic conductivity of the involved Na-rich NVO cathode. The cathode exhibits a high Mg2+ diffusion coefficient, and the resulting MSHIBs exhibit a power density of 3.4kW kg-1 and a lifespan of 20 000 cycles at 5.0 A g-1, with a capacity retention rate of 85%. Overall, this study paves the way for designing and developing fast-charging secondary batteries.

Anion vacancy engineering in carbon coating VS4 microspheres assembled by nanorod arrays for high-performance rechargeable Mg-Li hybrid batteries

Transition metal sulfides (TMSs) stand out as promising cathodes for rechargeable Mg-Li hybrid ion batteries (MLIBs) owing to their high theoretical capacity and rich redox chemistry. Nevertheless, it still faces great challenges involving the sluggish reaction kinetics and insufficient active sites, resulting in unsatisfactory stability and limited rate capability. And the role of anion vacancies on improving electrochemical properties of TMSs is still unclear. Herein, we have successfully designed an anion defect engineering strategy for the construction of carbon coating VS4 microspheres assembled by nanorod arrays (Sv-VS4@C-300) as the high-performance cathode for MLIBs. The systematic electrochemical tests together with theoretical calculations reveal that the sulfur vacancies simultaneously improve ion adsorption ability, facilitate charge transfer rate and boost reaction kinetics. Additionally, the open microsphere structure together with rich sulfur vacancies cooperatively provide more active sites and release the internal stress during cycling, thereby realizing the enhancement of capacity and structural stability. Consequently, these features enable Sv-VS4@C-300 with impressively high reversible capacity (485.1 mAh/g at 50 mA g−1) and exceptional long cycle lifespan (128.3 mAh/g at 2000 mA g−1 after 5000 cycles). This work implements an innovative strategy represented by anion vacancy engineering in the design of high-performance TMSs-based cathodes for rechargeable batteries.

Dual Strategy of Morphology Optimization and Interlayer Expansion in VS2 Cathode Toward High-Performance Mg-Li Hybrid Ion Batteries.

Combining the merits of the dendrite-free formation of a Mg anode and the fast kinetics of Li ions, the Mg-Li hybrid ion batteries (MLIBs) are considered an ideal energy storage system. However, the lack of advanced cathode materials limits their further practical application. Herein, we report a dual strategy of morphology optimization and interlayer expansion for the construction of hierarchical flower-like VS2 architecture coated by N-doped amorphous carbon layers. This tailored hierarchical flower-like structure coupled with homogeneous N-doped amorphous carbon layers cooperatively provide more active sites and buffer volume changes, thus realizing the enhancement of capacity and structural stability. Moreover, the enlarged interlayer spacing caused by the cointercalation of polyvinylpyrrolidone and ammonium ions can effectively promote the charge transfer rate and facilitate the rapid ion diffusion, as further demonstrated by electrochemical results and theoretical calculations. These features endow the hierarchical flower-like VS2 cathode with superior specific energy density (644.4 Wh kg-1, average voltage of 1.2 V vs Mg2+/Mg) and excellent rate capability (181.1 mAh g-1 at 2000 mA g-1). Systematic ex situ characterization measurements are employed to reveal the ion storage mechanism, which confirms that Li+ storage plays a leading role in the capacity contribution of MLIBs. Our strategy is in favor of providing useful insights to design and construct MLIBs with high energy density and excellent rate performance.

Tuning Electron Delocalization of Redox‐Active Porous Aromatic Framework for Low‐Temperature Aqueous Zn−K Hybrid Batteries with Air Self‐Chargeability

AbstractAir self‐charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self‐charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low‐temperature self‐charging aqueous Zn−K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)‐based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn‐ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all‐climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self‐charging process in the absence of an external power source. Impressively, the air self‐charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g−1), and exceptional self‐charging performance even at −40 °C. Therefore, the development of self‐charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Tuning Electron Delocalization of Redox-Active Porous Aromatic Framework for Low-Temperature Aqueous Zn-K Hybrid Batteries with Air Self-Chargeability.

Air self-charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self-charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low-temperature self-charging aqueous Zn-K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)-based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn-ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all-climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self-charging process in the absence of an external power source. Impressively, the air self-charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g-1), and exceptional self-charging performance even at -40 °C. Therefore, the development of self-charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Bi2S3 for aqueous copper ion battery based intercalation chemistry

Aqueous multivalent ion batteries have attracted increasing attention due to their high capacity, long cycle life, and impressive output energy. Considering that intercalation electrodes are more suitable for long cycle battery compared to the conversion ones, Cu2+ with appropriate ion radii has been chosen as intercalation carriers and bismuth sulfide with the matched lattice spacing as cathode to achieve long cycle life aqueous battery. We have synthesized the micrometer-scale flower-like Bi2S3 by regulating temperature and it is proved to be a perennial phase during Cu2+ intercalation/deintercalation of the Bi2S3 host when charge/discharge with a capacity of 104.5 mAh g–1 retention at 0.5 A g–1 after 1000 cycles. Lastly, build a hybrid ion battery with Zn and ZnSO4 electrolyte, the Bi2S3 cathode for Cu2+ intercalation can reach a maximum energy of 427.5 Wh Kg–1. The study provides a new intercalation cathode for aqueous multivalent ion batteries and will broaden the energy storage system.

A 3-V high-voltage and long-life magnesium-potassium hybrid ion battery

A 3-V high-voltage and long-life magnesium-potassium hybrid ion battery

High-performance magnesium/sodium hybrid ion battery based on sodium vanadate oxide for reversible storage of Na+ and Mg2+

Magnesium ion batteries (MIBs) are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation. Magnesium-sodium hybrid ion batteries (MSHBs) are an effective way to address these problems. Here, we report a new type of MSHBs that use layered sodium vanadate ((Na, Mn)V8O20·5H2O, Mn-NVO) cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) anode in Mg2+/Na+ hybrid electrolytes. During electrochemical cycling, Mg2+ and Na+ co-participate in the cathode reactions, and the introduction of Na+ promotes the structural stability of the Mn-NVO cathode, as cleared by several ex-situ characterizations. Consequently, the Mn-NVO cathode presents great specific capacity (249.9 mA h g−1 at 300 mA g−1) and cycling (1500 cycles at 1500 mA g−1) in the Mg2+/Na+ hybrid electrolytes. Besides, full battery displays long lifespan with 10,000 cycles at 1000 mA g−1. The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method, and the mechanism for these improvements is discussed.

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.

Multi-Ion Strategies Toward Advanced Rechargeable Batteries: Materials, Properties, and Prospects

As alternatives to conventional rocking-chair lithium-ion batteries (LIBs), novel rechargeable batteries utilizing abundant elements (such as sodium-ion batteries, potassium-ion batteries, and magnesium-ion batteries) have shown excellent performance. Nevertheless, these emerging batteries still face several challenges, including sluggish kinetics, limited reversibility, and a lack of suitable electrode materials. By incorporating carrier ions with different properties, hybrid-ion batteries (HIBs) based on multi-ion strategies have garnered extensive attention for their potential to solve most of these problems. However, with the increasing number of carrier ions that have been demonstrated to be suitable for multi-ion strategies, there exists deficiency in clarity regarding the nomenclature and classification of HIBs. For this reason, this comprehensive review offers an in-depth analysis of the fundamental configurations of HIBs according to the reaction mechanisms of the different carrier ions involved in the electrochemical redox reaction. Then, we systematically review the electrode materials for practical implementation on the basis of the energy storage mechanisms. Moreover, the challenges confronted by the current multi-ion strategies and promising future directions for overcoming these challenges are proposed for further research. The primary objective of this review is to inspire researchers in the rational design of highly efficient electrode materials for advanced HIBs.

A high-performance magnesium/lithium hybrid-ion battery using a hollow multi-layered NiS/Co3S4/carbon cathode and an all-phenyl-complex-based electrolyte.

Magnesium-lithium hybrid batteries (MLHBs) using a dual-ion electrolyte and safe Mg anode have promising potential for high-performance energy storage. Here, we develop an MLHB constructed of a hollow multi-layered NiS/Co3S4/carbon cathode and an all-phenyl-complex/lithium chloride (APC-LiCl) electrolyte. The hollow multi-layered structure and carbon matrix accommodate volumetric expansion and facilitate electrolyte penetration. The APC-LiCl electrolyte displays a stable electrochemical window. The MLHB shows a high specific capacity of 398 mA h g-1 after 100 cycles at 0.2 A g-1, and a stable capacity at 1.0 A g-1 after cycling 500 times. Moreover, stable rate performance and temperature tolerance are achievable. These findings would enable this design to be promising for developing other hybrid battery systems.

Ultralong-life and high-capacity magnesium/sodium hybrid-ion battery using a ternary CoSe/NiSe2/CuSe2 cathode and dual-ion electrolyte.

An ultrahigh-performance magnesium/sodium hybrid-ion battery (MNHB) is developed using ternary CoSe/NiSe2/CuSe2 (CNCS) "micro-flowers" as cathode materials, working with a coordinative [Mg2Cl2][AlCl4]2 and bis(trifluoroethylsulfonyl)imide anionic sodium salt in triglyme electrolyte. After 2000 cycles at 2.0 A g-1, the MNHB shows a stable capacity of 115.5 mA h g-1 and a high Coulombic efficiency exceeding 99.8%. The battery shows very rapid charging, and good stability in extreme environments, providing new opportunities to develop other hybrid-ion systems.

Highly improved aqueous Zn‖LiMn2O4 hybrid-ion batteries using poly(ethylene glycol) and manganese sulfate as electrolyte additives

Using a low dosage of poly(ethylene glycol) and MnSO4 for co-filling a bisalt electrolyte efficiently enhances the charging/discharging cycling performance of aqueous Zn‖LiMn2O4 batteries at relatively low current densities.

Engineering a high-capacity and long-cycle-life magnesium/lithium hybrid-ion battery using a lamellar SnSe2/SnSe/SnO2 cathode.

Since the safety and costs of current lithium-ion batteries are non-ideal, engineering a new energy-storage systems is needed. Magnesium/lithium hybrid-ion batteries (MLHBs) combining fast kinetics of Li ions and a dendrite-free Mg anode are promising. Here, we describe our development of an MLHB using lamellar SnSe2/SnSe/SnO2 as cathode material and an all-phenyl complex (APC)-based electrolyte. The multi-layered cathode material generated from a hierarchical precursor is conducive to diffusion of Li+ and Mg2+ ions, and buffers volumetric changes efficiently. After 2000 cycles at 1.0 A g-1, the battery shows a specific capacity of 233 mA h g-1 and a Coulombic efficiency of 100%. It also shows excellent rate performances. These findings suggest that the cathode design working with optimized electrolyte will find many applications for high-performance energy-storage systems.

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.

Investigations on Tunnel-Structure MnO2 for Utilization as a High-Voltage and Long-Life Cathode Material in Aqueous Ammonium-Ion and Hybrid-Ion Batteries.

Recently, nonmetal NH4 + ions have attracted extensive attention for use as charge carries in the field of energy storage due to their abundant resources, environmental friendliness, and low cost. However, the development of aqueous ammonium-ion batteries (AAIBs) is constrained by the absence of high-voltage and long-life materials. Herein, different tunnel-structure MnO2 materials (α-, β-, and γ-MnO2) are utilized as cathodes for AAIBs and hybrid-ion batteries and compared, and α-MnO2 is demonstrated to exhibit the most remarkable electrochemical performance. The α-MnO2 cathode material delivers the highest discharge capacity of 219mAhg-1 at a current density of 0.1Ag-1 and the best cyclability with a capacity retention of 95.4% after 10000 cycles at 1.0Ag-1. Moreover, aqueous ammonium-ion and hybrid-ion (ammonium/sodium ions) full batteries are successfully constructed using α-MnO2 cathodes. This work provides a novel direction for the development of aqueous energy storage for practical applications.

Aqueous aluminum-zinc hybrid ion batteries with urea-based hydrated eutectic electrolytes

Aqueous polyvalent ion batteries are more suitable for large-scale industrial applications than non-aqueous polyvalent ion batteries due to their intrinsic cost-effectiveness and eco-friendliness. Developing new electrolyte and finding compatible anode and cathode materials are key to improve battery performance and reversibility. Herein, we present a novel aluminum-urea hydrated eutectic electrolyte (AUHEE) by coupling Al2(SO4)3·18 H2O and urea. Urea-assisted hydrated aluminum ions weaken the strong interaction between aluminum ions and water molecules, thus inhibiting hydrogen precipitation and anode passivation by suppressing water dehydrogenation. Unique solvation structure of electrolyte enables the V2O5/AUHEE/Zn cell to exhibit high discharge capacity (250 mAh g−1) and long cycle life (1500 cycles), providing new insights into the development of aqueous polyvalent ion batteries with high performance.

In Situ Formed Amorphous Bismuth Sulfide Cathodes with a Self-Controlled Conversion Storage Mechanism for High Performance Hybrid Ion Batteries.

Conversion-type electrodes offer a promising multielectron transfer alternative to intercalation hosts with potentially high-capacity release in batteries. However, the poor cycle stability severely hinders their application, especially in aqueous multivalence-ion systems, which can fundamentally impute to anisotropic ion diffusion channel collapse in pristine crystals and irreversible bond fracture during repeated conversion. Here, an amorphous bismuth sulfide (a-BS) formed in situ with unprecedentedly self-controlled moderate conversion Cu2+ storage is proposed to comprehensively regulate the isotropic ion diffusion channels and highly reversible bond evolution. Operando synchrotron X-ray diffraction and substantive verification tests reveal that the total destruction of the Bi─S bond and unsustainable deep alloying are fully restrained. The amorphous structure with robust ion diffusion channels, unique self-controlled moderate conversion, and high electrical conductivity discharge products synergistically boosts the capacity (326.7 mAh g-1 at 1 A g-1 ), rate performance (194.5 mAh g-1 at 10 A g-1 ), and long-lifespan stability (over 8000 cycles with a decay rate of only 0.02 ‰ per cycle). Moreover, the a-BS Cu2+ ‖Zn2+ hybrid ion battery can well supply a stable energy density of 238.6Wh kg-1 at 9760W kg-1 . The intrinsically high-stability conversion mechanism explored on amorphous electrodes provides a new opportunity for advanced aqueous storage.

Chlorine doping endows Bi2Te3 with superior charge storage properties as a cathode material for high-performance aqueous zinc-proton hybrid ion batteries

To enhance the performance of aqueous batteries, researchers have introduced bismuth chalcogenides as cathode materials in zinc-based batteries. However, their ability to store charge is hindered by low electronic conductivity and poor ion adsorption capability. In this study, we fabricated Cl-doped Bi2Te3 (CBT) sheets through the hydrothermal tellurization of BiOCl plates. Density functional theory (DFT) calculations showed that CBT exhibits conductor-like electrical properties due to electronic structure manipulation. More importantly, the ion adsorption capability of CBT sheets was improved with the introduction of Cl dopant. Consequently, the CBT cathode demonstrated impressive rate capability, achieving a high capacity of 305 mA h g−1 at 0.2 A g−1, and sustaining a capacity of 124.7 mA h g−1 at 30 A g−1. Furthermore, after over 10,000 cycles at 20 A g−1, the reversible capacity remained at 115.8 mA h g−1, demonstrating exceptional cyclic stability.

Organic Composite Materials with Enhanced Cycling Stability and High-Rate Performance as Anodes for Aqueous Mg–Li Hybrid-Ion Batteries

Organic Composite Materials with Enhanced Cycling Stability and High-Rate Performance as Anodes for Aqueous Mg–Li Hybrid-Ion Batteries