Controlled Synthesis of SnO2 Nanostructures as Alloy Anode via Restricted Potential Toward Building High-Performance Dual-Ion Batteries with Graphite Cathode.

Dual-ion batteries (DIBs) are considered one of the promising energy storage devices in which graphite serves as a bi-functional electrode, i.e., anode and cathode in the aprotic organic solvents. Unlike conventional lithium-ion batteries (LIBs), DIBs reversibly store the cations and anions in the anode and cathodes during redox reactions, respectively. The electrolyte is a source for both cations and anions, so the choice of electrolyte plays a vital role. In the present work, the synthesis of SnO2 nanostructures is reported as a possible alternative for graphite anode, and the Li-storage performance is optimized in half-cell (Li/SnO2 ) assembly with varying amounts of conductive additive (acetylene black) and limited working potential (1 V vs Li). Finally, a DIB using recovered graphite (RG) fabricated from spent LIB as a cathode and SnO2 nanostructures as an anode under balanced loading conditions. Prior to the fabrication, both electrodes are pre-cycled to eliminate irreversibility. An in-situ impedance study has been employed to validate the passivation layer formation during the charge-discharge process. The high-performance SnO2 /RG-based DIB delivered a maximum discharge capacity of 380 mAh g-1 . The electrochemical performance of DIB has been assessed by varying temperature conditions to evaluate their suitability in different climatic conditions.

Regulation of Interfacial Chemistry Enabling High-Power Dual-Ion Batteries at Low Temperatures.

Interfacial chemistry plays a crucial role in determining the electrochemical properties of low-temperature rechargeable batteries. Although existing interface engineering has significantly improved the capacity of rechargeable batteries operating at low temperatures, challenges such as sharp voltage drops and poor high-rate discharge capabilities continue to limit their applications in extreme environments. In this study, an energy-level-adaptive design strategy for electrolytes to regulate interfacial chemistry in low-temperature Li||graphite dual-ion batteries (DIBs) is proposed. This strategy enables the construction of robust interphases with superior ion-transfer kinetics. On the graphite cathode, the design endues the cathode interface with solvent/anion-coupled interfacial chemistry, which yields an nitrogen/phosphor/sulfur/fluorin (N/P/S/F)-containing organic-rich interphase to boost anion-transfer kinetics and maintains excellent interfacial stability. On the Li metal anode, the anion-derived interfacial chemistry promotes the formation of an inorganic-dominant LiF-rich interphase, which effectively suppresses Li dendrite growth and improves the Li plating/stripping kinetics at low temperatures. Consequently, the DIBs can operate within a wide temperature range, spanning from -40 to 45 °C. At -40 °C, the DIB exhibits exceptional performance, delivering 97.4% of its room-temperature capacity at 1 C and displaying an extraordinarily high-rate discharge capability with 62.3% capacity retention at 10 C. This study demonstrates a feasible strategy for the development of high-power and low-temperature rechargeable batteries.

A donor-acceptor (D-A) conjugated polymer for fast storage of anions.

Organic electrode materials have attracted a lot interest in batteries in recent years. However, most of them still suffer from low performance such as low electrode potential, slow reaction kinetics, and short cycle life. In this work, we report a strategy of fabricating donor-acceptor (D-A) conjugated polymers for facilitating the charge transfer and therefore accelerating the reaction kinetics by using the copolymer (p-TTPZ) of dihydrophenazine (PZ) and thianthrene (TT) as a proof-of-concept. The D-A conjugated polymer as p-type cathode could store anions and exhibited high discharge voltages (two plateaus at 3.82 V, 3.16 V respectively), a reversible capacity of 152 mAh g-1 at 0.1 A g-1 , excellent rate performance with a high capacity of 124.2 mAh g-1 at 10 A g-1 (≈50 C) and remarkable cyclability. The performance, especially the rate capability was much higher than that of its counterpart homopolymers without D-A structure. As a result, the p-TTPZ//graphite full cells showed a high output voltage (3.26 V), a discharge specific capacity of 139.1 mAh g-1 at 0.05 A g-1 and excellent rate performance. This work provides a novel strategy for developing high performance organic electrode materials through molecular design and will pave a way towards high energy density organic batteries.

Insight into the Role of Fluoroethylene Carbonate on the Stability of Sb||Graphite Dual-Ion Batteries in Propylene Carbonate-Based Electrolyte.

Sodium dual-ion batteries (Na-DIBs) have attracted increasing attention due to their high operative voltages and low-cost raw materials. However, the practical applications of Na-DIBs are still hindered by the issues, such as low capacity and poor Coulombic efficiency, which is highly correlated with the compatibility between electrode and electrolyte but rarely investigated. Herein, fluoroethylene carbonate (FEC) is introduced into the electrolyte to regulate cation/anion solvation structure and the stability of cathode/anode-electrolyte interphase of Na-DIBs. The FEC modulates the environment of PF6 - solvation sheath and facilitates the interaction of PF6 - on graphite. In addition, the NaF-rich interphase caused by the preferential decomposition of FEC effectively inhibits side reactions and pulverization of anodes with the electrolyte. Consequently, Sb||graphite full cells in FEC-containing electrolyte achieve an improved capacity, cycling stability and Coulombic efficiency. This work elucidates the underlying mechanism of bifunctional FEC and provides an alternative strategy of building high-performance dual ion batteries.

Unlocking Four-electron Conversion in Tellurium Cathodes for Advanced Magnesium-based Dual-ion Batteries.

Magnesium (Mg) batteries hold promise as a large-scale energy storage solution, but their progress has been hindered by the lack of high-performance cathodes. Here, we address this challenge by unlocking the reversible four-electron Te0/Te4+ conversion in elemental Te, enabling the demonstration of superior Mg//Te dual-ion batteries. Specifically, the classic magnesium aluminum chloride complex (MACC) electrolyte is tailored by introducing Mg bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2), which initiates the Te0/Te4+ conversion with two distinct charge-storage steps. Te cathode undergoes Te/TeCl4 conversion involving Cl- as charge carriers, during which a tellurium subchloride phase is presented as an intermediate. Significantly, the Te cathode achieves a high specific capacity of 543 mAh gTe -1 and an outstanding energy density of 850 Wh kgTe -1, outperforming most of the previously reported cathodes. Our electrolyte analysis indicates that the addition of Mg(TFSI)2 reduces the overall ion-molecule interaction and mitigates the strength of ion-solvent aggregation within the MACC electrolyte, which implies the facilized Cl- dissociation from the electrolyte. Besides, Mg(TFSI)2 is verified as an essential buffer to mitigate the corrosion and passivation of Mg anodes caused by the consumption of the electrolyte MgCl2 in Mg//Te dual-ion cells. These findings provide crucial insights into the development of advanced Mg-based dual-ion batteries.

2D Conjugated Metal-Organic Frameworks Bearing Large Pore Apertures and Multiple Active Sites for High-Performance Aqueous Dual-Ion Batteries.

2D conjugated metal-organic frameworks (2D c-MOFs) with large pore sizes and high surface areas are advantageous for adsorbing iodine species to enhance the electrochemical performance of aqueous dual-ion batteries (ADIBs). However, most of the reported 2D c-MOFs feature microporous structures, with few examples exhibiting mesoporous characteristics. Herein, we developed two mesoporous 2D c-MOFs, namely PA-TAPA-Cu-MOF and PA-PyTTA-Cu-MOF, using newly designed arylimide based multitopic catechol ligands (6OH-PA-TAPA and 8OH-PA-PyTTA). Notably, PA-TAPA-Cu-MOF exhibits the largest pore sizes (3.9 nm) among all reported 2D c-MOFs. Furthermore, we demonstrated that these 2D c-MOFs can serve as promising cathode host materials for polyiodides in ADIBs for the first time. The incorporation of triphenylamine moieties in PA-TAPA-Cu-MOF resulted in a higher specific capacity (423.4 mAh g-1 after 100 cycles at 1.0 A g-1) and superior cycling performance, retaining 96 % capacity over 1000 cycles at 10 A g-1 compared to PA-PyTTA-Cu-MOF. Our comparative analysis revealed that the increased number of N anchoring sites and larger pore size in PA-TAPA-Cu-MOF facilitate efficient anchoring and conversion of I3 -, as supported by spectroscopic electrochemistry and density functional theory calculations.

On-Water Surface Synthesis of Vinylene-Linked Cationic Two-Dimensional Polymer Films as the Anion-Selective Electrode Coating.

Vinylene-linked two-dimensional polymers (V-2DPs) and their layer-stacked covalent organic frameworks (V-2D COFs) featuring high in-plane π-conjugation and robust frameworks have emerged as promising candidates for energy-related applications. However, current synthetic approaches are restricted to producing V-2D COF powders that lack processability, impeding their integration into devices, particularly within membrane technologies reliant upon thin films. Herein, we report the novel on-water surface synthesis of vinylene-linked cationic 2DPs films (V-C2DP-1 and V-C2DP-2) via Knoevenagel polycondensation, which serve as the anion-selective electrode coating for highly-reversible and durable zinc-based dual-ion batteries (ZDIBs). Model reactions and theoretical modeling revealed the enhanced reactivity and reversibility of the Knoevenagel reaction on the water surface. On this basis, we demonstrated the on-water surface 2D polycondensation towards V-C2DPs films that show large lateral size, tunable thickness, and high chemical stability. Representatively, V-C2DP-1 presents as a fully crystalline and face-on oriented film with in-plane lattice parameters of a=b≈43.3 Å. Profiting from its well-defined cationic sites, oriented 1D channels, and stable frameworks, V-C2DP-1 film possesses superior bis(trifluoromethanesulfonyl)imide anion (TFSI-)-transport selectivity (transference, t_=0.85) for graphite cathode in high-voltage ZDIBs, thus triggering additional TFSI--intercalation stage and promoting its specific capacity (from ~83 to 124 mAh g-1) and cycling life (>1000 cycles, 95 % capacity retention).

Ultrafast Charge and Long Life of High-Voltage Cathodes for Dual-Ion Batteries via a Bifunctional Interphase Nanolayer on Graphite Particles.

Dual-ion batteries (DIBs) with Co/Ni-free cathodes especially graphite cathodes are very attractive energy storage systems in the long run because of the cost effectiveness and sustainability. However, graphite cathodes severely suffer from poor structural stability during anions storage at high potentials owing to the oxidative decomposition of electrolytes and volume expansion. This work proposes an artificial cathode/electrolyte interphase (CEI) strategy by implanting polyphosphoric acid (PPA) nanofilms tightly on natural graphite (NG) particles via interfacial hydrogen bonding. The electrochemical results show that the PPA-modified graphite cathodes possess enhanced charge-discharge reversibility, accelerated electrode reaction kinetic, decreased resistance, decelerated self-discharge, and prolonged cycling life. Through post-analyses on the cycled graphite cathodes, the improved performance is mainly attributed to the PPA-based CEI, which effectively mitigates the electrolyte decomposition and protects the graphitic structure. More interestingly, the hydrogen bonding interactions between poly(vinyldifluoride) (PVDF) binder and PPA as validated through density functional theory calculations and practical experiments can increase the contact sites of PVDF chains on NG@PPA particles. Meanwhile, the cross-linking effect of PPA can enhance the mechanical strength of PVDF, thus the long life of NG@PPA cathode is also correlated with the improved mechanical stability of the entire electrode.

Anion-Vacancy Modified WSSe Nanosheets on 3D Cross-Networked Porous Carbon Skeleton for Non-Aqueous Sodium-Based Dual-Ion Storage.

Sodium-based dual-ion batteries (SDIBs) have become a new type of energy storage device with great application value because of their high operating voltage, high energy density, and low cost. However, transition-metal dichalcogenide (TMD) anodes show unsatisfactory Na+ electrochemical performance owing to the low intrinsic conductivity and inferior ion transport kinetics. Here, an elaborate design is developed to prepare a composite of WSSe nanosheets supported on a 3D cross-networked porous carbon skeleton (WSSe@CPCS), which possesses en-rich anion vacancies and WSSe with expanded inter-layer spacing, as well as an interconnected porous structure. As a result, the WSSe@CPCS anode for sodium-ion batteries (SIBs) exhibits preeminent reversible capacities, excellent cycle stability, and superior rate capability. The systematic electrochemical kinetic analysis and density functional theory results further show that the effect of anion vacancies and CPCS synergistically enhances the conductivity and reduces charge transfer resistance, thus making a great contribution to fast reaction kinetics. Finally, the implementations of the WSSe@CPCS anode in progressive SIB and DIB full-cell configurations exhibit satisfactory performance, which reveals their widely practical application. This research will provide an exciting approach to designing advanced defect-structured tungsten-based TMD materials for SIBs, DIBs, and even a broad range of energy storage.

Carbon Electrode Materials for Advanced Potassium-Ion Storage.

Tremendous progress has been made in the field of electrochemical energy storage devices that rely on potassium-ions as charge carriers due to their abundant resources and excellent ion transport properties. Nevertheless, future practical developments not only count on advanced electrode materials with superior electrochemical performance, but also on competitive costs of electrodes for scalable production. In the past few decades, advanced carbon materials have attracted great interest due to their low cost, high selectivity, and structural suitability and have been widely investigated as functional materials for potassium-ion storage. This article provides an up-to-date overview of this rapidly developing field, focusing on recent advanced and mechanistic understanding of carbon-based electrode materials for potassium-ion batteries. In addition, we also discuss recent achievements of dual-ion batteries and conversion-type K-X (X=O2 , CO2 , S, Se, I2 ) batteries towards potential practical applications as high-voltage and high-power devices, and summarize carbon-based materials as the host for K-metal protection and possible directions for the development of potassium energy-related devices as well. Based on this, we bridge the gaps between various carbon-based functional materials structure and the related potassium-ion storage performance, especially provide guidance on carbon material design principles for next-generation potassium-ion storage devices.

Large Interlayer Distance and Heteroatom-Doping of Graphite Provide New Insights into the Dual-Ion Storage Mechanism in Dual-Carbon Batteries.

Dual-ion batteries (DIBs) is a promising technology for large-scale energy storage. However, it is still questionable how material structures affect the anion storage behavior. In this paper, we synthesis graphite with an ultra-large interlayer distance and heteroatomic doping to systematically investigate the combined effects on DIBs. The large interlayer distance of 0.51 nm provides more space for anion storage, while the doping of the heteroatoms reduces the energy barriers for anion intercalation and migration and enhances rapid ionic storage at interfaces simultaneously. Based on the synergistic effects, the DIBs composed of carbon cathode and lithium anode afford ultra-high capacity of 240 mAh g-1 at current density of 100 mA g-1 . Dual-carbon batteries (DCBs) using the graphite as both of cathode and anode steadily cycle 2400 times at current density of 1 A g-1 . Hence, this work provides a reference to the strategy of material designs of DIBs and DCBs.

Calcium Based All-Organic Dual-Ion Batteries with Stable Low Temperature Operability.

In response to the application requirements of secondary batteries at low temperature, an all-organic dual-ion battery with calcium perchlorate contained acetonitrile as the electrolyte (CAN-ODIB) is fabricated in this work. The electrochemical energy is stored in CAN-ODIB via the association and disassociation of calcium and perchlorate ions in perylene diimide-ethylene diamine/carbon black composite based anode and polytriphenylamine based cathode with highly reversible redox states. Benefiting from the energy storage mechanism, CAN-ODIB exhibits excellent electrochemical performances in tests with the temperature ranging from 25 to -50 °C. Especially, CAN-ODIB at -50 °C reserves ≈61% of the capacity at 25 °C (83.4 mA h g-1 ) with the current density of 0.2 A g-1 . CAN-ODIB also shows excellent cycling stability at low temperature by retaining 90.3% of the initial capacity at 1.0 A g-1 after 450 charge-discharge cycles at -30 °C. The impedance analysis of CAN-ODIB at different temperatures indicates that the low temperature performance of CAN-ODIB depends more on the electrode materials than the electrolyte, which provides the important guidance for the further design of secondary batteries operable at low temperatures.

Rational Design Strategy of Novel Energy Storage Systems: Toward High-Performance Rechargeable Magnesium Batteries.

Rechargeable magnesium batteries (RMBs) are promising candidates to replace currently commercialized lithium-ion batteries (LIBs) in large-scale energy storage applications owing to their merits of abundant resources, low cost, high theoretical volumetric capacity, etc. However, the development of RMBs is still facing great challenges including the incompatibility of the electrolyte and the lack of suitable cathode materials with high reversible capacity and fast kinetics of Mg2+ . While tremendous efforts have been made to explore compatible electrolytes and appropriate electrode materials, the rational design of unconventional Mg-based battery systems is another effective strategy for achieving high electrochemical performance. This review specifically discusses the recent research progress of various Mg-based battery systems. First, the optimization of electrolyte and electrode materials for conventional RMBs is briefly discussed. Furthermore, various Mg-based battery systems, including Mg-chalcogen (S, Se, Te) batteries, Mg-halogen (Br2 , I2 ) batteries, hybrid-ion batteries, and Mg-based dual-ion batteries are systematically summarized. This review aims to provide a comprehensive understanding of different Mg-based battery systems, which can inspire latecomers to explore new strategies for the development of high-performance and practically available RMBs.

Fluorination Treatment of Conjugated Protonated Polyanilines for High-Performance Sodium Dual-Ion Batteries.

The overall performance of dual-ion batteries (DIBs) is strongly linked to anions storage properties of cathodes. Whereas high energy/power densities and stabilities for DIBs are limited by cathodes. To overcome these barriers, we have designed a novel fluoridized-polyaniline-H+ /carbon nanotubes (FPHC) as cathode for high-efficiency PF6 - storage. F- in PF6 - is easy to form covalent bond with H on -NH- in FPHC, so that PF6 - can stably coordinate with FPHC, showing a symmetrical structure. FPHC cathode shows a highly reversible capacity of 73 mAh g-1 at 2 A g-1 after 2000 cycles, which provides a solid base for the advanced sodium dual-ion batteries (SDIBs) (310 Wh kg-1 /7720 W kg-1 ). Besides, the relative pouch-type SDIB can drive a vacuum cleaner model with an electric machine. This work may shed light on an up-and-coming strategy of robust cathodes for SDIBs.

Vacant Manganese-Based Perovskite Fluorides@Reduced Graphene Oxides for Na-Ion Storage with Pseudocapacitive Conversion/Insertion Dual Mechanisms.

Na-ion capacitors (NICs) and Na-based dual-ion batteries (Na-DIBs) have been considered to be promising alternatives to traditional lithium-ion batteries (LIBs) because of the abundance and low cost of the Na-ion, but their energy density, power density and life cycle are limited. Herein, dual-vacancy (including K+ and F- vacancies) perovskite fluoride K0.86 MnF2.69 @reduced graphene oxide (rGO; recorded as Mn-G) as anode for NICs and Na-DIBs has been developed. The special conversion/intercalation dual Na-ion energy storage mechanism and pseudocapacitive dynamics are analyzed in detail. The Mn-G//AC NICs and Mn-G//KS6 Na-DIBs delivered a maximum energy density of 92.7 and 187.6 W h kg-1 , a maximum power density of 20.2 and 21.12 kW kg-1 , and long cycle performance of 61.3 and 68.4 % after 1000 cycles at 5 A g-1 , respectively. Moreover, Mn-G//AC NICs and Mn-G//KS6 Na-DIBs can work well over a wide range of temperatures (-20 to 40 °C). These results make it competitive in Na-ion storage applications with high energy/power density over a wide temperature range.

Locally Ordered Graphitized Carbon Cathodes for High-Capacity Dual-Ion Batteries.

Dual-ion batteries (DIBs) inherently suffer from limited energy density. Proposed here is a strategy to effectively tackle this issue by employing locally ordered graphitized carbon (LOGC) cathodes. Quantum mechanical modeling suggests that strong anion-anion repulsions and severe expansion at the deep-charging stage raise the anion intercalation voltage, therefore only part of the theoretical anion storage sites in graphite is accessible. The LOGC interconnected with disordered carbon is predicted to weaken the interlaminar van der Waals interactions, while disordered carbons not only interconnect the dispersed nanographite but also partially buffer severe anion-anion repulsion and offer extra capacitive anion storage sites. As a proof-of-concept, ketjen black (KB) with LOGC was used as a model cathode for a potassium-based DIB (KDIB). The KDIB delivers an unprecedentedly high specific capacity of 232 mAh g-1 at 50 mA g-1 , a good rate capability of 110 mAh g-1 at 2000 mA g-1 , and excellent cycling stability of 1000 cycles without obvious capacity fading.

A TiSe2 -Graphite Dual Ion Battery: Fast Na-Ion Insertion and Excellent Stability.

The sodium dual ion battery (Na-DIB) technology is proposed as highly promising alternative over lithium-ion batteries for the stationary electrochemical energy-storage devices. However, the sluggish reaction kinetics of anode materials seriously impedes their practical implementation. Herein, a Na-DIB based on TiSe2 -graphite is reported. The high diffusion coefficient of Na-ions (3.21×10-11 -1.20×10-9  cm2 s-1 ) and the very low Na-ion diffusion barrier (0.50 eV) lead to very fast electrode kinetics, alike in conventional surface capacitive storage systems. In-situ investigations reveal that the fast Na-ion diffusion involves four insertion stage compositions. A prototype cell shows a reversible capacity of 81.8 mAh g-1 at current density of 100 mA g-1 , excellent stability with 83.52 % capacity retention over 200 cycles and excellent rate performance, suggesting its potential for next-generation large scale high-performance stationary energy storage systems.

A Tetrakis(terpyridine) Ligand-Based Cobalt(II) Complex Nanosheet as a Stable Dual-Ion Battery Cathode Material.

Inspired by the flexibility of the bottom-up approach in terms of selecting molecular components and thus tailoring functionalities, a terpyridine derivative (1,2,4,5-tetrakis(4-(2,2':6',2″-terpyridyl)phenyl)benzene) (Tetra-tpy) is synthesized and coordinated with Co(II) ion to self-assemble into a nanosheet Co-sheet by a facile interface-assisted synthesis. The bis(terpyridine)-Co(II) complex nanosheet formed not only shows good stability, but also features the layered structure and rich electrochemical activity inherited from the embedded Co(terpyridine)2 motif. Thus, Co-sheet can serve as a cathode material for a dual-ion battery prototype, which exhibits a high utilization of redox-active sites, good cycling stability, and rate capability, thus expanding the potential application of this kind of easily prepared metal-complex nanosheets in the field of energy storage.

Dual-Carbon Batteries: Materials and Mechanism.

Various carbon nanomaterials are being widely studied for applications in supercapacitors and Li-ion batteries as well as hybrid energy storage devices. Dual-carbon batteries (DCBs), in which both electrodes are composed of functionalized carbon materials, are capable of delivering high energy/power and stable cycles when they are rationally designed. This Review focuses on the electrochemical reaction mechanisms and energy storage properties of various carbon electrode materials in DCBs, including graphite, graphene, hard and soft carbon, activated carbon, and their derivatives. The interfacial chemistry between carbon electrodes and electrolyte is also discussed. The perspective for further development of DCBs is presented at the end.

Hybrid Aqueous/Nonaqueous Water-in-Bisalt Electrolyte Enables Safe Dual Ion Batteries.

Dual ion batteries (DIBs) have recently attracted ever-increasing attention owing to the potential advantages of low material cost and good environmental friendliness. However, the potential safety hazards, cost, and environmental concerns mainly resulted from the commonly used nonaqueous organic solvents severely hinder the practical application of DIBs. Herein, a hybrid aqueous/nonaqueous water-in-bisalt electrolyte with both broad electrochemical stability window and excellent safety performance is developed. The lithium-based DIB assembled using KS6 graphite and niobium pentoxide as the active materials in the cathode and anode exhibits good comprehensive performance including capacity, cycling stability, rate performance, and medium discharge voltage. Initial capacities of ≈47.6 and 29.6 mAh g-1 retention after 300 cycles can be delivered with a medium discharge voltage of around 2.2 V in the voltage window of 0-3.2 V at the current density of 200 mA g-1 . Good rate performance for the battery can be indicated by 29.7 mAh g-1 discharge capacity retention at 400 mA g-1 . It is noteworthy that the coulombic efficiency of the battery can reach as high as 93.9%, which is comparable to that of the corresponding DIBs using nonaqueous organic electrolytes.