Charting the course to solid-state dual-ion batteries

An electrolyte destined for use in a dual-ion battery(DIB)must be stable at the inherently high potential required for anion intercalation in the graphite electrode,while also protecting the Al current collector from anodic dissolution.A higher salt concentration is needed in the electrolyte,in comparison to typical battery electrolytes,to maximize energy density,while ensuring acceptable ionic conductivity and operational safety.In recent years,studies have demonstrated that highly concentrated organic electrolytes,ionic liquids,gel polymer electrolytes(GPEs),ionogels,and water-in-salt electrolytes can potentially be used in DIBs.GPEs can help reduce the use of solvents and thus lead to a substantial change in the Coulombic efficiency,energy density,and long-term cycle life of DIBs.Furthermore,GPEs are suited to manufacture compact DIB designs without separators by virtue of their mechanical strength and electrical performance.In this review,we highlight the latest advances in the application of different electrolytes in DIBs,with particular emphasis on GPEs.

Upcycling the spent graphite/LiCoO_(2) batteries for high-voltage graphite/LiCoPO_(4)-co-workable dual-ion batteries

The worldwide proliferation of portable electronics has resulted in a dramatic increase in the number of spent lithium-ion batteries(LIBs).However,traditional recycling methods still have limitations because of such huge amounts of spent LIBs.Therefore,we proposed an ecofriendly and sustainable double recycling strategy to concurrently reuse the cathode(LiCoO_(2))and anode(graphite)materials of spent LIBs and recycled LiCoPO_(4)/graphite(RLCPG)in Li^(+)/PF^(-)_(6) co-de/intercalation dual-ion batteries.The recycle-derived dualion batteries of Li/RLCPG show impressive electrochemical performance,with an appropriate discharge capacity of 86.2 mAh·g^(-1) at25 mA·g^(-1) and 69%capacity retention after 400 cycles.Dual recycling of the cathode and anode from spent LIBs avoids wastage of resources and yields cathode materials with excellent performance,thereby offering an ecofriendly and sustainable way to design novel secondary batteries.

Anion Defects Engineering of Ternary Nb-Based Chalcogenide Anodes Toward High-Performance Sodium-Based Dual-Ion Batteries

Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIBs featuring with high kinetics and long durability. Herein, we report the design and fabrication of N-doped carbon film-modified niobium sulfur–selenium(NbSSe/NC) nanosheets architecture, which holds favorable merits for Na^(+) storage of enlarged interlayer space, improved electrical conductivity, as well as enhanced reaction reversibility, endowing it with high capacity, high-rate capability and high cycling stability. The combined electrochemical studies with density functional theory calculation reveal that the enriched defects in such nanosheets architecture can benefit for facilitating charge transfer and Na+ adsorption to speed the electrochemical kinetics. The NbSSe/NC composites are studied as the anode of a full SDIBs by pairing the expanded graphite as cathode, which shows an impressively cyclic durability with negligible capacity attenuation over 1000 cycles at 0.5 A g^(-1), as well as an outstanding energy density of 230.6 Wh kg^(-1) based on the total mass of anode and cathode.

Coral-like and binder-free carbon nanowires for potassium dual-ion batteries with superior rate capability and long-term cycling life

Owing to the advantages of high operating voltage,environmental benignity,and low cost,potassium-based dual-ion batteries(KDIBs)have been considered as a potential candidate for large-scale energy storage.However,KDIBs generally suffer from poor cycling performance and unsatisfied capacity,and inactive components of conductive agents,binders,and current collector further lower their overall capacity.Herein,we prepare coral-like carbon nanowres(CCNWs)doped with nitrogen as a binder-free anode material for K^(+)-ion storage,in which the unique coral-like porous nanostructure and amorphous/short-range-ordered composite feature are conducive to enhancing the structural stability,to facilitating the ion transfer and to boosting the full utilization of active sites during potassiation/de-potassiation process.As a result,the CCNW anode possesses a hybrid K^(+)-storage mechanism of diffusive behavior and capacitive adsorption,and stably delivers a high capacity of 276 mAh g^(-1)at 50 mA g^(-1),good rate capability up to 2 A g^(-1),and long-term cycling stability with 93%capacity retention after 2000 cycles at 1 A g^(-1).Further,assembling this CCNW anode with an environmentally benign expanded graphite(EG)cathode yields a proof-of-concept KDIB,which shows a high specific capacity of 134.4 mAh g^(-1)at 100 mA g^(-1),excellent rate capability of 106.5 mAh g^(-1)at 1 A g^(-1),and long-term cycling stability over 1000 cycles with negligible capacity loss.This study provides a feasible approach to developing high-performance anodes for potassium-based energy storage devices.

Dual-Ion Co-Regulation System Enabling High-Performance Electrochemical Artificial Yarn Muscles with Energy-Free Catch States

Artificial yarn muscles show great potential in applications requiring low-energy consumption while maintaining high performance. However, conventional designs have been limited by weak ion-yarn muscle interactions and inefficient “rocking-chair” ion migration. To address these limitations, we present an electrochemical artificial yarn muscle design driven by a dual-ion co-regulation system. By utilizing two reaction channels, this system shortens ion migration pathways, leading to faster and more efficient actuation. During the charging/discharging process, PF_6~- ions react with carbon nanotube yarn, while Li~+ ions react with an Al foil. The intercalation reaction between PF_6~- and collapsed carbon nanotubes allows the yarn muscle to achieve an energy-free high-tension catch state. The dual-ion coordinated yarn muscles exhibit superior contractile stroke, maximum contractile rate, and maximum power densities, exceeding those of “rocking-chair” type ion migration yarn muscles. The dual-ion co-regulation system enhances the ion migration rate during actuation, resulting in improved performance. Moreover, the yarn muscles can withstand high levels of isometric stress, displaying a stress of 61 times that of skeletal muscles and 8 times that of “rocking-chair” type yarn muscles at higher frequencies. This technology holds significant potential for various applications, including prosthetics and robotics.

Green and sustainably designed intercalation-type anodes for emerging lithium dual-ion batteries with high energy density

Lithium dual-ion batteries(LiDIBs)have attracted significant attention owing to the growing demand for modern anode materials with high energy density.Herein,rust encapsulated in graphite was achieved by utilizing ammonium bicarbonate(ABC)as a template,which resulted in mesoporous Fe3O4embedded in expanded carbon(Fe3O4@G(ABC))via simple ball milling followed by annealing.This self-assembly approach for graphite-encapsulated Fe3O4composites helps enhance the electrochemical performance,such as the cycling stability and superior rate stability(at 3 A/g),with improved conductivity in Li DIBs.Specifically,Fe3O4@G-1:4(ABC)and Fe3O4@G-1:6(ABC)anodes in a half-cell at 0.1 A/g delivered initial capacities of 1390.6 and 824.4 mA h g^(-1),respectively.The optimized anode(Fe3O4@G-1:4(ABC))coupled with the expanded graphite(EG)cathode in Li DIBs provided a substantial initial specific capacity of 260.9 mA h g^(-1)at 1 A/g and a specific capacity regain of 106.3 mA h g^(-1)(at 0.1 A/g)after 250 cycles,with a very high energy density of 387.9 Wh kg^(-1).The strategically designed Fe3O4@G accelerated Li-ion kinetics,alleviated the volume change,and provided an efficient conductive network with excellent mechanical flexibility,resulting in exceptional performance in Li DIBs.Various postmortem analyses of the anode and cathode(XRD,Raman,EDS,and XPS)are presented to explain the intercalation-type electrochemical mechanisms of Li DIBs.This study offers several advantages,including safety,low cost,sustainability,environmental friendliness,and high energy density.

Carbon foam with microporous structure for high performance symmetric potassium dual-ion capacitor

A novel carbon foam with microporous structure(CFMS),with the advantages of a simple fabrication process,low energy consumption,large specific surface area and high conductivity,has been prepared by a facile one-step carbonization.In addition,the carbon foam possesses suitable interlayer spacing in short range which is flexible to accommodate the deformation of carbon layer caused by the ion insertion and deinsertion at the charge and discharge state.Furthermore,a low cost carbon-based symmetric potassium dual-ion capacitor(PDIC),which integrates the virtues of potassium ion capacitors and dual-ion batteries,is successfully established with CFMS as both the battery-type cathode and the capacitor-type anode.PDIC displays a superior rate performance,an ultra-long cycle life(90%retention after 10000 cycles),and a high power density of 7800 W kg^-1 at an energy density of 39Whkg^-1.The PDIC also exhibits excellent ultrafast charge and slow discharge properties,with a full charge in just 60 s and a discharge time of more than 3000 s.

Integrated Co3O4/carbon fiber paper for high-performance anode of dual-ion battery

In dual-ion batteries (DIBs), energy storage is achieved by intercalation/de-intercalation of both cations and anions. Due to the mismatch between ion diameter and layer space of active materials, however, volume expansion and exfoliation always occur for electrode materials. Herein, an integrated electrode Co3O4/carbon fiber paper (CFP) is prepared as the anode of DIB. As the Co3O4 nanosheets grow on CFP substrate vertically, it promotes the immersion of electrolyte and shortens the pathway for ionic transport. Besides, the strong interaction between Co3O4 and CFP substrate reduces the possibility of sheet exfoliation. An integrated-electrode-based DIB is therefore packaged using Co3O4/CFP as anode and graphite as cathode. As a result, a high energy density of 72 Wh/kg is achieved at a power density of 150 W/kg. The design of integrated electrode provides a new route for the development of high-performance DIBs.

3D skeleton nanostructured Ni_3S_2/Ni foam@RGO composite anode for high-performance dual-ion battery

The growing global demands of safe, low-cost and high working voltage energy storage devices trigger strong interests in novel battery concepts beyond state-of-art lithium-ion battery. Herein, a dualion battery based on nanostructured Ni_3S_2/Ni foam@RGO(NSNR) composite anode is developed, utilizing graphite as cathode material and LiPF6-VC-based solvent as electrolyte. The battery operates at high working voltage of 4.2–4.5 V, with superior discharge capacity of ～90 m A h g^(-1) at 100 mA g^(-1), outstanding rate performance, and long-term cycling stability over 500 cycles with discharge capacity retention of ～85.6%. Moreover, the composite simultaneously acts as the anode material and the current collector, and the corrosion phenomenon can be greatly reduced compared to metallic Al anode. Thus, this work represents a significant step forward for practical safe, low-cost and high working voltage dual-ion batteries,showing attractive potential for future energy storage application.

Unlock the potential of Li4Ti5O(12) for high-voltage/long-cycling-life and high-safety batteries: Dual-ion architecture superior to lithium-ion storage

Li4Ti5O(12)(LTO)has drawn great attention due to its safety and stability in lithium-ion batteries(LIBs).However,high potential plateau at 1.5 V vs.Li reduces the cell voltage,leading to a limited use of LTO.Dual-ion batteries(DIBs)can achieve high working voltage due to high intercalation potential of cathode.Herein,we propose a DIB configuration in which LTO is used as anode and the working voltage was 3.5 V.This DIB achieves a maximum specific energy of 140 Wh/kg at a specific power of 35 W/kg,and the specific power of 2933 W/kg can be obtained with a remaining specific energy of 11 Wh/kg.Traditional LIB material shows greatly improved properties in the DIB configuration.Thus,reversing its disadvantage leads to upgraded performance of batteries.Our configuration has also widened the horizon of materials for DIBs.

Feasible engineering of cathode electrolyte interphase enables the profoundly improved electrochemical properties in dual-ion battery

Dual-ion battery(DIB) composed of graphite cathode and lithium anode is regarded as an advanced secondary battery because of the low cost, high working voltage and environmental friendliness. However,DIB operated at high potential(usually ≥ 4.5 V versus Li+/Li) is confronted with severe challenges including electrolyte decomposition on cathode interface, and structural deterioration of graphite accompanying with anions de-/intercalation, hinder its cyclic life. To address those drawbacks and preserve the DIB virtues, a feasible and scalable surface modification is achieved for the commercial graphite cathode of mesocarbon microbead. In/ex-situ studies reveal that, such an interfacial engineering facilitates and reconstructs the formation of chemically stable cathode electrolyte interphase with better flexibility alleviating the decomposition of electrolyte, regulating the anions de-/intercalation behavior in graphite with the retainment of structural integrity and without exerting considerable influence on kinetics of anions diffusion. As a result, the modified mesocarbon microbead exhibits a much-extended cycle life with high capacity retention of 82.3% even after 1000 cycles. This study demonstrates that the interface modification of electrode and coating skeleton play important roles on DIB performance improvement, providing the feasible basis for practical application of DIB owing to the green and scalable coating procedures.

Concurrent recycling chemistry for cathode/anode in spent graphite/LiFePO_(4) batteries:Designing a unique cation/anion-co-workable dual-ion battery

With the increasing popularity of new en ergy electric vehicles,the dema nd for lithium-ion batteries(LIBs)has been growing rapidly,which will produce a large number of spent LIBs.Therefore,recycling of spe nt LIBs has become an urge nt task to be solved,otherwise it will inevitably lead to serious environmental pollution.Herein,a unique recycling strategy is proposed to achieve the concurrent reuse of cathode and anode in the spent graphite/LiFePO_(4) batteries.Along with such recycling process,a unique cathode composed of recycled LFP/graphite(RLFPG)with cation/anion-co-storage ability is designed for new-type dual-ion battery(DIB).As a result,the recycle-derived DIB of Li/RLFPG is established with good electrochemical performance,such as an initial discharge capacity of 117.4 mA h g^(-1) at 25 mA g^(-1) and 78% capacity retention after 1000 cycles at 100 mA g^(-1).The working mechanism of Li/RLFPG DIB is also revealed via in situ X-ray diffraction and electrode kinetics studies.This work not only presents a farreaching significance for large-scale recycling of spent LIBs in the future,but also proposed a sustainable and econo mical method to design n ew-type sec on dary batteries as recycling of spe nt LIBs.

Recent advances and perspectives of fluorite and perovskite-based dual-ion conducting solid oxide fuel cells

High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and solid oxide electrolysis cells for H_(2) production from water electrolysis or CO_(2) electrochemical reduction to value-added chemicals.In particular,internal diffusion of protons or oxygen ions is a fundamental and crucial issue in the research of SOFCs,hypothetically based on either oxygen-ionconducting electrolytes or proton-conducting electrolytes.Up to now,some electrolyte materials based on fluorite or perovskite structure were found to show certain degree of dual-ion transportation capability,while in available electrolyte database,particularly in the field of SOFCs,such dual-ion conductivity was seriously overlooked.Actually,few concerns arising to the simultaneous proton and oxygen-ion conductivities in electrolyte of SOFCs inevitably induce various inadequate and confusing results in literature.Understanding dual-ion transportation behavior in electrolyte is indisputably of great importance to explain some unusual fuel cell performance as reported in literature and enrich the knowledge of solid state ionics.On the other hand,exploration of novel dual-ion conducting electrolytes will benefit the development of SOFCs.In this review,we provide a comprehensive summary of the understanding of dual-ion transportation in solid electrolyte and recent advances of dual-ion conducting SOFCs.The oxygen ion and proton conduction mechanisms at elevated temperature inside oxide-based electrolyte materials are first introduced,and then(mixed) oxygen ion and proton conduction behaviors of fluorite and perovskite-type oxides are discussed.Following on,recent advances in the development of dual-ion conducting SOFCs based on fluorite and perovskite-type single-phase or composite electrolytes,are reviewed.Finally,the challenges in the development of dual-ion conducting SOFCs are discussed and future prospects are proposed.

Nitrogen-rich hierarchically porous carbon foams as high-performance electrodes for lithium-based dual-ion capacitor

Nitrogen-rich porous carbonaceous materials have shown great potential in energy storage and conversion applications due to their facile fabrication,high electronic conductivity,and improved hydrophilic property.Herein,three-dimensional porous N-rich carbon foams are fabricated through a one-step carbonization-activation method of the commercial melamine foam,and displaying hierarchically porous structure(macro-,meso-,and micro-pores),large surface area(1686.5 m2 g^-1),high N-containing level(3.3 at%),and excellent compressibility.The as-prepared carbon foams as electrodes for quasi-solid-state supercapacitors exhibit enhanced energy storage ability with 210 F g^-1 and 2.48c at 0.1 A g^-1,and150 F g^-1 and 1.77 F cm^-2 at 1 A g^-1,respectively.Moreover,as an electrode for lithium-based dual-ion capacitor,this distinctive porous carbon also delivers remarkable specific capacitance with 143.6 F g^-1 at0.1 A g^-1 and 116.2 F g^-1 at 1 A g^-1.The simple preparation method and the fascinating electrochemical performance endow the N-rich porous carbon foams great prospects as high-performance electrodes for electrochemical energy storage.

Dual-ion hybrid supercapacitor:Integration of Li-ion hybrid supercapacitor and dual-ion battery realized by porous graphitic carbon

Lithium-ion hybrid supercapacitors(Li-HSCs) and dual-ion batteries(DIBs) are two types of energy storage devices that have attracted extensive research interest in recent years. Li-HSCs and DIBs have similarities in device structure, tendency for ion migration, and energy storage mechanisms at the negative electrode. However, these devices have differences in energy storage mechanisms and working potentials at the positive electrode. Here, we first realize the integration of a Li-HSC and a DIB to form a dual-ion hybrid supercapacitor(DIHSC), by employing mesocarbon microbead(MCMB)-based porous graphitic carbon(PGC) with a partially graphitized structure and porous structure as a positive electrode material. The MCMB-PGC-based DIHSC exhibits a novel dual-ion battery-capacitor hybrid mechanism: it exhibits excellent electronic double-layer capacitor(EDLC) behavior like a Li-HSC in the low-middle wide potential range and anion intercalation/de-intercalation behavior like a DIB in the high-potential range. Two types of mechanisms are observed in the electrochemical characterization process, and the energy density of the new DIHSC is significantly increased.

Identifying Heteroatomic and Defective Sites in Carbon with Dual-Ion Adsorption Capability for High Energy and Power Zinc Ion Capacitor

Aqueous zinc-based batteries(AZB s)attract tremendous attention due to the abundant and rechargeable zinc anode.Nonetheless,the requirement of high energy and power densities raises great challenge for the cathode development.Herein we construct an aqueous zinc ion capacitor possessing an unrivaled combination of high energy and power characteristics by employing a unique dual-ion adsorption mechanism in the cathode side.Through a templating/activating co-assisted carbonization procedure,a routine protein-rich biomass transforms into defect-rich carbon with immense surface area of 3657.5 m^(2) g^(-1) and electrochemically active heteroatom content of 8.0 at%.Comprehensive characterization and DFT calculations reveal that the obtained carbon cathode exhibits capacitive charge adsorptions toward both the cations and anions,which regularly occur at the specific sites of heteroatom moieties and lattice defects upon different depths of discharge/charge.The dual-ion adsorption mechanism endows the assembled cells with maximum capacity of 257 mAh g^(-1) and retention of72 mAh g^(-1) at ultrahigh current density of 100 A g^(-1)(400 C),corresponding to the outstanding energy and power of 168 Wh kg^(-1)and 61,700 W kg^(-1).Furthermore,practical battery configurations of solid-state pouch and cable-type cells display excellent reliability in electrochemistry as flexible and knittable power sources.

A bipolar metal phthalocyanine complex for sodium dual-ion battery

Dual-ion batteries(DIBs) have attracted immense interest as a new generation of energy storage device due to their low cost,environmental friendliness and high working voltage.However,developing DIBs using organic compounds as active electrode materials is in its infancy.Herein,we first report a bipolar and self-polymerized Cu phthalocyanine(CuTAPc) as an electrode material for sodium-based DIBs(SDIBs).Benefitting from the bipolar property,CuTAPc could serve as the cathode or anode material to construct metal sodium-based or metal sodium-free SDIB(cell 1 or 2) by coupling with sodium anode or graphite cathode,respectively.As a result,cell 1 displays a high discharge capacity of 195.7 mAh g^(-1) at 50 mA g^(-1) and a high reversible capacity of 57 mAh g^(-1) over 2500 cycles at 1 A g^(-1),and cell 2 shows a high energy density of 324 Wh kg^(-1) and a high power density of 7481 W kg^(-1).Subsequently,the proposed binding mechanism and the bipolar reactivity of CuTAPc have been revealed by the detailed reaction kinetic analysis and ex-situ techniques as well as the density functional theory(DFT) calculations.This work could open a pathway to develop the advanced SDIBs constructed by elemental abundant and environmentally friendly organic materials.

Boosting the kinetics of PF_(6)^(-) into graphitic layers for the optimal cathode of dual-ion batteries:The rehearsal of pre-intercalating Li^(+)

Large anions exhibit slow diffusion kinetics in graphite cathode of dual-ion batteries(DIBs);particularly at high current density,it suffers severely from the largely-reduced interlayer utilization of graphite cathode,which as a bottleneck limits the fast charge application of DIBs.To maximize interlayer utilization and achieve faster anion diffusion kinetics,a fast and uncrowded anion transport channel must be established.Herein,Li^(+)was pre-intercalated into the graphite paper(GP)cathode to increase the interlayer spacing,and then hosted for the PF_(6)^(-)anion storage.Combined with theoretical calculation,it shows that the local interlayer spacing enlargement and the residual Li^(+)reduce the anion intercalation energy and diffusion barrier,leading to better rate stability.The obtained GP with Li^(+)pre-intercalation(GP-Li)electrode exhibits a discharge capacity of 23.1 m Ah g^(-1) at a high current of 1300 m A g^(-1).This work provides a facile method to efficiently improve the interlayer utilization of graphite cathode at large currents.

An all-organic aqueous potassium dual-ion battery

Benefiting from the environmental friendliness of organic electrodes and the high security of aqueous electrolyte,an all-organic aqueous potassium dual-ion full battery(APDIB) was assembled with 21 M potassium bis(fluoroslufonyl)imide(KFSI) water-in-salt as the electrolyte.The APDIB could deliver a reversible capacity of around 50 mAh g^(-1) at 200 mA g^(-1)(based on the weight of total active materials),a long cycle stability over 900 cycles at 500 mA g^(-1) and a high coulombic efficiency of 98.5%.The reaction mechanism of APDIB during the charge/discharge processes is verified:the FSI-could associate/disassociate with the nitrogen atom in the polytriphenylamine(PTPAn) cathode,while the K^(+) could react with C=O bonds in the 3,4,9,10-perylenetetracarboxylic diimide(PTCDI) anode reversibly.Our work contributes toward the understanding the nature of water-into-salt electrolyte and successfully constructed all-organic APDIB.

A review of halide charge carriers for rocking-chair and dual-ion batteries

This review discusses how halide ion species have been used as charge carriers in both anion rocking-chair and dual-ion battery(DIB)systems.The anion rocking-chair batteries based on fluoride and chloride have emerged over the past decade and are garnering increased research interest due to their large theoretical energy density values and the natural abundance of halide-containing materials.Moreover,DIBs that use halide species as their anionic charge carrier are seen as one of the promising next-generation battery technologies due to their low cost and high working potentials.Although numerous polyatomic anions have been studied as charge carriers,the use of single halide ions(i.e.,F−and Cl−)and metal-based superhalides(e.g.,[MgCl_(3)]−)as anionic charge carriers in DIBs has been considerably less explored.Herein,we provide an overview of some of the key advances and recent progress that has been made with regard to halide ion charge carriers in electrochemical energy storage.We offer our perspectives on the current state of the field and provide a roadmap in hopes that it helps researchers toward making new advances in these promising and emerging areas.