Dual-ion Batteries Research Articles

Ternary Ionogel Electrolytes Enable Quasi‐Solid‐State Potassium Dual‐Ion Intercalation Batteries

Dual-Ion Batteries A novel battery concept reliant on a dual-ion intercalation mechanism is demonstrated in article 2100122 by Antonia Kotronia, Habtom Desta Asfaw, and co-workers. Using glass fiber fabrics infused with an ionogel electrolyte, a compact dual-ion battery (DIB) is demonstrated. The potassium-based salts used in the electrolyte make the DIB attractive for storing energy from renewable sources.

A montmorillonite-modification strategy enabling long cycling stability of dual-ion batteries.

Lithium‖graphite dual-ion batteries (DIBs) have received widespread attention due to their low cost and high operating voltage (nearly 5 V). However, DIBs face several challenges such as decomposition of the electrolyte under high voltage and structural deterioration of graphite. Herein, montmorillonite (MMT) is employed to generate a favorable and robust cathode electrolyte interface (CEI) layer on the graphite surface. As a result, the DIBs exhibit a 100% capacity retention for 500 cycles at 2C. Even after 1000 cycles at 5C, the capacity retention is still as high as 99%.

Electrochemical Activity Regulating by Strain Control to Achieve High-Performance Potassium-Ion-Based Dual-Ion Battery

Electrochemical Activity Regulating by Strain Control to Achieve High-Performance Potassium-Ion-Based Dual-Ion Battery

Rechargeable hybrid organic Zn battery (ReHOZnB) with non-flammable electrolyte

ReHOB has been constructed by adopting intrinsically safe organic electrolyte through the replacement of the traditional aqueous electrolyte that displayed good cycling stability with TTFP additive. • Aqueous electrolytes for Zn anode have been replaced by TMP based electrolyte. • The strategy addressed safety concerns along with high Zn reversibility. • Zn/Na 2 Mn[Fe(CN) 6 ] battery exhibited excellent stability with TTFP- additive. Zn-based rechargeable batteries suffer from thermodynamic instability of Zn anode in aqueous electrolytes that results in low Coulombic efficiencies (CEs) and decreased anode reversibility. Therefore, as an alternative, non-aqueous Zn-battery chemistry has gained significant attention in the recent times that can effectively resolve the issues of thermodynamic instability along with improvement in CE of Zn plating/stripping. However, the adoption of organic electrolytes over aqueous ones throws a serious safety challenge. In this work, traditional aqueous electrolytes have been replaced by an intrinsically safe organic electrolyte in dual-ion Zn batteries to construct a rechargeable hybrid organic Zn battery (ReHOZnB) that effectively addresses the safety concerns along with providing highly reversible Zn anode. The Zn/ Na 2 Mn[Fe(CN) 6 ] (Na 2 MnHCf) battery delivered a reversible capacity of 89.3 mAh g −1 at a C-rate of 1 (1C = 160 mA g −1 ) exhibiting long term cycling stability with a capacity retention of 77% (66%) after 1000 (2000) charge–discharge cycles. The cycling performance has been stabilized through in-situ generation of cathode electrolyte interphase (CEI). This works provides an alternate electrolyte for the development of safe Zn batteries.

A fast and stable sodium-based dual-ion battery achieved by Cu3P@P-doped carbon matrix anode

Sodium-based dual-ion batteries (SDIBs) are of great interest as promising candidates for large-scale energy storage due to the advantages of low cost, high cell voltage, and eco-friendliness. However, their practical applications are restricted by the unsatisfactory rate and cycling performance resulted from the sluggish Na + reaction kinetics of anode materials. Herein, a novel SDIB is developed by using Cu 3 P particles confined in conductive P-doped carbon layers (Cu 3 P@PC) as the anode for the first time. The rational designed architecture of Cu 3 P@PC accelerates Na + diffusion kinetics and alleviates volume variation effects, which endows the as-assembled Cu 3 P@PC//expanded graphite (EG) SDIB outstanding performance. The device delivers good rate performance up to 30 C at an upper cutoff voltage of 5.0 V, excellent cycling stability with a capacity retention of 94% over 900 cycles at 10 C, among the best results of the reported SDIBs. • A fast and stable sodium-based dual-ion battery was achieved by Cu 3 P@PC anode. • Cu 3 P was anchored in a P-doped carbon via a calcination process of Cu-HEDP. • The Cu 3 P@PC shows high Na + diffusion kinetics and alleviated volume variation.

Using Amorphous Cosx Hollow Nanocages as Cathodes for High-Performance Magnesium-Lithium Dual-Ion Batteries

Using Amorphous Cosx Hollow Nanocages as Cathodes for High-Performance Magnesium-Lithium Dual-Ion Batteries

Cobalt and oxygen double doping induced C@MoS2–CoS2–O@C nanocomposites with an improved electronic structure and increased active sites as a high-performance anode for sodium-based dual-ion batteries

Cobalt and oxygen double doping induced C@MoS2–CoS2–O@C nanocomposites has been synthesized. The special structure improves electronic structure, increases active sites and possesses superior electrochemical performance.

Regulation of Dual-Ion Batteries Via the Defects Design in Carbon Electrode Based on the Different Storage Behaviors of Pf6- and Li+

Regulation of Dual-Ion Batteries Via the Defects Design in Carbon Electrode Based on the Different Storage Behaviors of Pf6- and Li+

A novel high-energy-density lithium-free anode dual-ion battery and in situ revealing the interface structure evolution.

Lithium-free anode dual-ion batteries have attracted extensive studies due to their simple configuration, reduced cost, high safety and enhanced energy density. For the first time, a novel Li-free DIB based on a carbon paper anode (Li-free CGDIB) is reported in this paper. Carbon paper anodes usually have limited application in DIBs due to their poor electrochemical performance. Herein, by using a lithium bis(fluorosulfonyl)imide (LiFSI)-containing electrolyte, the battery shows outstanding electrochemical performance with a capacity retention of 96% after 300 cycles at 2C with a stable 98% coulombic efficiency and 89% capacity retention after 500 cycles at 5C with a stable coulombic efficiency of 98.5%. Moreover, the electrochemical properties of the CGDIB were investigated with a variety of in situ characterization techniques, such as in situ EIS, XRD and online differential electrochemical mass spectrometry (OEMS). The multifunctional effect of the LiFSI additive on the electrochemical properties of the Li-free CGDIB was also systematically analyzed, including generating a LiF-rich interfacial film, prohibiting Li dendrite growth effectively and forming a defective structure of graphite layers. This design strategy and fundamental analysis show great potential and lay a theoretical foundation for facilitating the further development of DIBs with high energy density.

Te-Doping Induced C@Mos2-Xtex@C One-Dimensional Nanocomposites with Improved Electronic Structure and Enlarged Interlayer Spacing as High-Performance Anode for Sodium-Based Dual-Ion Batteries

Te-Doping Induced C@Mos2-Xtex@C One-Dimensional Nanocomposites with Improved Electronic Structure and Enlarged Interlayer Spacing as High-Performance Anode for Sodium-Based Dual-Ion Batteries

Chaotropic anion based “water-in-salt” electrolyte realizes a high voltage Zn–graphite dual-ion battery

We report a high voltage Zn–graphite dual-ion battery based on Zn(ClO4)2 water-in-salt (WiS) electrolyte with a wide electrochemical window of 2.80 V and high oxidative stability of 2.60 V vs. Zn/Zn2+.

A High‐Performance Dual‐Ion Battery‐Supercapacitor Hybrid Device Based on LiCl in Ion Liquid Dual‐Salt Electrolyte

AbstractA dual‐ion battery‐supercapacitor hybrid device (DIB‐SCHD), cleverly integrating a dual‐ion battery (DIB) and a supercapacitor (SC), is expected to endow both the high energy density of dual‐ion battery and the high power density of supercapacitor. Benefitting from the similar features of the electrolyte and symmetrical electrode configuration, a state‐of‐the‐art DIB‐SCHD is developed by using N‐doped micropores‐dominant carbon(N‐MPC) as the electrode and LiCl in a room‐temperature ion liquid hybrid as the electrolyte, which deliver an ultrahigh mass capacitance of 374 F g−1 with a high voltage of 3.5 V and a remarkable specific energy of 208 Wh kg−1 at 1144 W kg−1 and an ultrahigh specific power of 22834 W kg−1 at 77 Wh kg−1. Combined with ex situ characterizations and theoretical calculations, the assembled DIB‐SCHD presents a synergistic energy storage mechanism simultaneously involving ion intercalation/deintercalation and adsorption/desorption processes, which can promote the reaction kinetics and achieve exceptional electrochemical performance. The perfect integration of the dual‐ion battery‐type and supercapacitor‐type electrodes provides a new strategy toward high energy and power density electrochemical energy storage devices.

Realizing the Multi-electron Reaction in the Na3V2(PO4)3 Cathode via Reversible Insertion of Dihydrogen Phosphate Anions.

Dual-ion battery (DIB) is an up-and-coming technology for the energy storage field. However, most of the current cathodes are still focused on the graphite hosts, which deliver a limited specific capacity. In this work, we demonstrated for the first time that H2PO4- can be used as the charge carrier for Na3V2(PO4)3 under an aqueous electrolyte, which enabled the V3+/V4+ and V4+/V5+ multielectron reactions in the Na3V2(PO4)3 electrode. The fabricated aqueous DIB delivers a high average voltage of ∼0.75 V (vs Ag/AgCl) and a high capacity of 280.7 mA h g-1. Moreover, the formed V5+-based novel cathode exhibits a capacity of 170.2 mA h g-1 in an organic sodium-ion battery. This study may open a new direction for fabricating high-voltage electrodes through the design of DIBs.

Reversible anion intercalation into graphite from aluminum perchlorate “water‐in‐salt” electrolyte

Anion intercalated graphite has achieved tremendous attention for the application as cathode materials in dual-ion batteries due to their high working potentials, reversibility, and low cost. However, the process of anion intercalation into graphite requires high oxidative stability of the electrolytes and high reaction potentials above 1.4 V vs. Ag/AgCl (4.5 V vs. Li+). Reaching such high potentials is difficult with conventional aqueous electrolytes due to their limited electrochemical window. Here, we demonstrate a highly concentrated “water-in-salt” electrolyte of aluminum perchlorate that demonstrates a wide electrochemical stability window of 4.0 V. The “water-in-salt” electrolyte suppresses the dissociation of water at high potentials, facilitating a stable and reversible perchlorate (ClO4−) anion intercalation into the graphite with a Coulombic efficiency of over 95% for more than 2000 cycles. The structural and chemical changes of the anion-intercalated graphite are studied by Operando Raman, Operando X-ray diffraction, and X-ray photoelectron spectroscopy. Our study provides an insight into ClO4− anion intercalation into graphite in the supersaturated aluminum perchlorate “water-in-salt” electrolyte, demonstrating a suitable platform for future high-voltage aqueous energy storage systems.

A polymeric cathode-electrolyte interface enhances the performance of MoS2-graphite potassium dual-ion intercalation battery

Anion intercalation in the graphite cathode of a dual-ion battery (DIB) occurs at unusually high voltage (>4.5 V K + /K). This exacerbates electrolyte degradation and corrosion of Al current collectors, leading to poor coulombic efficiency (CE), typically <90%, and short cell life as a result. These limitations can be mitigated if a stable cathode-electrolyte interface layer (CEI) can form on the graphite electrode. In this study, we demonstrate that the performance of a potassium-based DIB can be improved with a triallyl phosphate (TAP) monomer added in 6 m KN(SO 2 CF 3 ) 2 (KTFSI)-dimethyl carbonate (DMC) electrolyte. The TAP additive forms a stable polymeric CEI on the graphite particles and thus increases the CE of the cell to 97%–99%. Together with MoS 2 -negative electrodes with a pre-formed solid electrolyte interphase (SEI) layer, the DIB concept has been shown to offer specific capacities from ∼40 to 80 mAh g −1 with an average discharge voltage of 3.7 V. • Design principle for high-performance MoS 2 -graphite dual-ion battery is proposed • Impact of electrolyte additives on the negative and positive electrodes is investigated • Triallyl phosphate is used to generate a polymeric CEI on graphite cathode • MoS 2 with pre-formed SEI layer ensures stable cycling and high coulombic efficiency A dual-ion battery operates at unusually high voltage, which is needed to intercalate anions in a graphite cathode. Asfaw et al. explore strategies to create more stable electrode-electrolyte interfaces in an effort to design potassium-based MoS 2 -natural-graphite dual-ion battery with high coulombic efficiency and long cycle life.

Insights into self-induced electrochemical activation of carbon cathode

Continuous capacity increase in electrochemical cycling, termed as electrochemical activation, is a frequently observed but rarely systematically studied phenomenon. Such phenomenon is noted in a preliminary study of carbon cathode for dual ion battery, showing gradual discharge capacity growth from 186 mAh g−1 (the 1st) to 320 mAh g−1 (the 300th). Systematical characterizations are carried out to investigate this phenomenon occurred on the carbon cathode, hydrothermally reduced graphene oxide (HrGO). The electrochemical activation comes from surface area increment, originated from multilayer reduced graphene oxide rolls formation and accumulation and structural order increase in cycling. The formation of rolls is plausibly a result of strain release of reduced graphene layers after electrochemical interaction with PF6−. Additionally, charge storage mechanism of HrGO is revealed. At active surface sites of HrGO, PF6− is consistently stored in a pseudocapacitive manner. In contrast, at well-crystallized domains, pseudocapacitive PF6− uptake occurs at low voltage region while PF6− intercalation dominates at higher potentials. Supportive lithium storage also contributes to total capacity. Comprehensively, this work offers valuable insights of electrochemical activation and carbon cathodes’ electrochemical behaviors and will facilitate the construction of high-capacity carbon cathodes.

Advanced cathode for dual-ion batteries: Waste-to-wealth reuse of spent graphite from lithium-ion batteries

The amount of spent lithium-ion batteries (LIBs) is constantly increasing as their popularity grows. It is important to develop a recycling method that cannot only convert large amounts of waste anode graphite into high value-added products but is also simple and environmentally friendly. In this work, spent graphite from an anode was transformed into a cathode for dual-ion batteries (DIBs) through a two-step treatment. This method enables the crystal structure and morphology of spent graphite to recover from the adverse effects of long cycling and be restored to a regular layered structure with appropriate layer spacing for anion intercalation. In addition, pyrolysis of the solid electrolyte interphase into an amorphous carbon layer prevents the electrode from degrading and improves its cycling performance. The recycled negative graphite has a high reversible capacity of 87 mAh g−1 at 200 ​mA ​g−1, and its rate performance when used as a cathode in DIBs is comparable to that of commercial graphite. This simple recycling idea turns spent anode graphite into a cathode material with attractive potential and superior electrochemical performance, genuinely achieving sustainable energy use. It also provides a new method for recovering exhausted batteries.

Polypyrrole as an ultrafast organic cathode for dual-ion batteries

Organic electrode materials based on the chemical bond cleavage/recombination working principle usually produce unimpressive reaction kinetics and stability. In this work, polypyrrole (PPy) is investigated as an ultrafast (87% retention at 20 ​A ​g−1) and stable (83% retention across 3000 cycles) cathode material in PPy|graphite dual-ion batteries. The fast intrinsic reaction kinetics, coupled with a capacitance-dominated mechanism, enable PPy to bypass the sluggish chemical bond rearrangement process. Electrochemically induced secondary doping improves the ordered aggregation of polymer chains and thus has a profound impact on anion diffusion and electrical conductivity. The excellent rate capability presented here changes our understanding of organic electrode materials and could prove useful for designing ultrafast rechargeable electrochemical devices.

Tuning anion chemistry enables high-voltage and stable potassium-based tellurium-graphite batteries

Potassium-based dual-ion batteries (KDIBs) are promising large-scale energy-storage devices due to cost benefits, high output voltage, and abundant K resources, but their advancements are restricted by alternative anodes, low-capacity graphite cathode, and electrolyte decomposition. Herein, high-voltage and stable KDIBs composed of tellurium-decorated porous carbon nanosheets (TeCNs) anode and graphite cathode are constructed by regulating salt types and electrolyte concentrations. Compared with potassium hexafluorophosphate/carbonate electrolytes, high-concentrated potassium bis(fluorosulfonyl)imide (KFSI)-based electrolytes enable high capacity and cyclability of graphite cathode. The weak anion-solvent interaction avoids solvent co-intercalation, whereas the strong coordination of K+-FSI−-carbonate complexes facilitates antioxidation and interphase stability. By inheriting the excellent K+-ion storage of TeCNs and electrochemical compatibility with the 4.0 m electrolyte, Te-graphite KDIBs deliver a high discharge voltage plateau of 4.37 V, the capacity of 130.8 mAh g−1 after 500 cycles, and high-power densities. This work discloses the important roles of ion-solvent pairs, and provides clear guidelines for electrolyte design in DIBs.

The Free-Standing Alloy Strategy to Improve the Electrochemical Performance of Potassium-Based Dual-Ion Batteries

The Free-Standing Alloy Strategy to Improve the Electrochemical Performance of Potassium-Based Dual-Ion Batteries