A Review of Anode Materials for Dual‑Ion Batteries

Distinct from"rockingchair"lithium-ion batteries(LIBs),the unique anionic intercalation chemistry on the cathode side of dual-ion batteries(DIBs)endows them with intrinsic advantages of low cost,high voltage,and ecofriendly,which is attracting widespread attention,and is expected to achieve the next generation of large-scale energy storage applications.Although the electrochemical reactions on the anode side of DIBs are similar to that of LIBs,in fact,to match the rapid insertion kinetics of anions on the cathode side and consider the compatibility with electrolyte system which also serves as an active material,the anode materials play a very important role,and there is an urgent demand for rational structural design and performance optimization.A review and summarization of previous studies will facilitate the exploration and optimization of DIBs in the future.Here,we summarize the development process and working mechanism of DIBs and exhaustively categorize the latest research of DIBs anode materials and their applications in different battery systems.Moreover,the structural design,reaction mechanism and electrochemical performance of anode materials are briefly discussed.Finally,the fundamental challenges,potential strategies and perspectives are also put forward.It is hoped that this review could shed some light for researchers to explore more superior anode materials and advanced systems to further promote the development of DIBs.

A review of anode materials for sodium ion batteries

Lithium-ion batteries(LIBs)are used in electric vehicles and portable smart devices,but lithium resources are dwindling and there is an increasing demand which has to be catered for.Sodium ion batteries(SIBs),which are less costly,are a promising replacement for LIBs because of the abundant natural reserves of sodium.The anode of a SIB is a necessary component of the battery but is less understood than the cathode.This review outlines the development of various types of anodes,including carbonbased,metallic and organic,which operate using different reaction mechanisms such as intercalation,alloying and conversion,and considers their challenges and prospects.Strategies for modifying their structures by doping and coating,and also modifying the solid electrolyte interface are discussed.In addition,this review also discusses the challenges encountered by the anode of SIBs and the solutions.

Polypyrrole-coated triple-layer yolk-shell Fe_(2)O_(3)anode materials with their superior overall performance in lithium-ion batteries

Iron oxide(Fe_(2)O_(3))emerges as a highly attractive anode candidate among rapidly expanding energy storage market.Nonethe-less,its considerable volume changes during cycling as an electrode material result in a vast reduced battery cycle life.In this work,an ap-proach is pioneered for preparing high-performance Fe_(2)O_(3)anode materials,by innovatively synthesizing a triple-layer yolk-shell Fe_(2)O_(3)uniformly coated with a conductive polypyrrole(Ppy)layer(Fe_(2)O_(3)@Ppy-TLY).The uniform polypyrrole coating introduces more reac-tion sites and adsorption sites,and maintains structure stability through charge-discharge process.In the uses as lithium-ion battery elec-trodes,Fe_(2)O_(3)@Ppy-TLY demonstrates high reversible specific capacity(maintaining a discharge capacity of 1375.11 mAh·g^(−1)after 500 cycles at 1 C),exceptional cycling stability(retaining the steady charge-discharge performance at 544.33 mAh·g^(−1)after 6000 ultrafast charge-discharge cycles at a 10 C current density),and outstanding high current charge-discharge performance(retaining a reversible ca-pacity of 156.75 mAh·g^(−1)after 10000 cycles at 15 C),thereby exhibiting superior lithium storage performance.This work introduces in-novative advancements for Fe_(2)O_(3)anode design,aiming to enhance its performance in energy storage fields.

Two-dimensional layered In_(2)P_(3)S_(9): A novel superior anode material for sodium-ion batteries

Developing reliable and efficient anode materials is essential for the successfully practical application of sodium-ion batteries.Herein,employing a straightforward and rapid chemical vapor deposition technique,two-dimensional layered ternary indium phosphorus sulfide(In_(2)P_(3)S_(9)) nanosheets are prepared.The layered structure and ternary composition of the In_(2)P_(3)S_(9) electrode result in impressive electrochemical performance,including a high reversible capacity of 704 mA h g^(-1) at 0.1 A g^(-1),an outstanding rate capability with 425 mA h g^(-1) at 5 A g^(-1),and an exceptional cycling stability with a capacity retention of88% after 350 cycles at 1 A g^(-1).Furthermore,sodium-ion full cell also affords a high capacity of 308 and114 mA h g^(-1) at 0.1 and 5 A g^(-1).Ex-situ X-ray diffraction and ex-situ high-resolution transmission electron microscopy tests are conducted to investigate the underlying Na-storage mechanism of In_(2)P_(3)S_(9).The results reveal that during the first cycle,the P-S bond is broken to form the elemental P and In_(2)S_(3),collectively contributing to a remarkably high reversible specific capacity.The excellent electrochemical energy storage results corroborate the practical application potential of In_(2)P_(3)S_(9) for sodium-ion batteries.

Review and prospects on the low-voltage Na_(2)Ti_(3)O_(7) anode materials for sodium-ion batteries

Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in improving the energy density of NIBs.Low-voltage anode materials,however,are severely lacking in NIBs.Of all the reported insertion oxides anodes,the Na_(2)Ti_(3)O_(7) has the lowest operating voltage(an average potential of 0.3 V vs.Na^(+)/Na)and is less likely to deposit sodium,which has excellent potential for achieving NIBs with high energy densities and high safety.Although significant progress has been made,achieving Na_(2)Ti_(3)O_(7) electrodes with excellent performance remains a severe challenge.This paper systematically summarizes and discusses the physicochemical properties and synthesis methods of Na_(2)Ti_(3)O_(7).Then,the sodium storage mechanisms,key issues and challenges,and the optimization strategies for the electrochemical performance of Na_(2)Ti_(3)O_(7) are classified and further elaborated.Finally,remaining challenges and future research directions on the Na_(2)Ti_(3)O_(7) anode are highlighted.This review offers insights into the design of high-energy and high-safety NIBs.

A class of Ga-Al-P-based compounds with disordered lattice as advanced anode materials for Li-ion batteries

Phosphides possess large reversible capacity, small voltage hysteresis, and high energy efficiency, thus promising to be new anode candidates to replace commercial graphite for Li-ion batteries(LIBs).Through a facile mechanochemistry method, we prepare a novel ternary phosphide of Ga0.5Al0.5P whose crystalline structure is determined to be a cation-disordered cubic zinc sulfide structure according to XRD refinement. As an anode for LIBs, the Ga0.5Al0.5P delivers a reversible capacity of 1,352 mA h g^(-1)at100 mA g^(-1)with an initial Coulombic efficiency(ICE) up to 90.0% based on a reversible Li-storage mechanism integrating intercalation and subsequent conversion processes as confirmed by various characterizations techniques including in-situ XRD, ex-situ Raman, and XPS and electrochemical characterizations.Graphite-modified Ga0.5Al0.5P exhibits a long-lasting cycling stability of retaining 1,182 mA h g^(-1)after300 cycles at 100 m A g^(-1), and 625 mA h g^(-1)after 800 cycles at 2,000 mA g^(-1), and a high-rate performance of remaining 342 m A h g^(-1)at 20,000 mA g^(-1). The outstanding electrochemical performances can be attributed to enhanced reaction kinetics enabled by the capacitive behaviors and the faster Liion diffusion enabled by the cation-mixing. Importantly, by tuning the cationic ratio, we develop a novel series of cation-mixed compounds of Ga_(1/3)Al_(2/3)P, Ga_(1/4)Al_(3/4)P, Ga_(1/5)Al_(4/5)P, Ga_(2/3)Al_(1/3)P, Ga_(3/4)Al_(1/4)P, and Ga_(4/5)Al_(1/5)P, which demonstrate large capacity, high ICE, and suitable anode potentials. Broadly, these compounds with disordered lattices probably present novel physicochemical properties, and high electrochemical performances, thus providing a new perspective for new materials design.

Two-dimensional MOF-based materials:Preparations and applications as electrodes in Li-ion batteries

Two-dimensional(2D)metal-organic frameworks(MOFs)are rapidly emerging as a unique class of mushrooming family of 2D materials offering distinctive features,such as hierarchical porosity,extensive surface area,easily available active sites,and versatile,adaptable structures.These promising characteristics have positioned them as highly appealing alternatives for a wide range of applications in energy storage technologies,including lithium batteries.Nevertheless,the poor conductivity and limited stability of 2D MOFs have limited their real applications in electrochemical energy storage.These limitations have therefore warranted ongoing research to enhance the performance of 2D MOFs.Given the significance of 2D MOF-based materials as an emerging class of advanced materials,a multitude of strategy has been devised to address these challenges such as synthesizing 2D conductive MOFs and derivatives along with 2D MOF hybridization.One promising approach involves the use of 2D MOF derivatives,including transition metal oxides,which due to their abundant unsatu rated active metal sites and shorter diffusion paths,offer superior electrochemical performance.Additionally,by combining pristine 2D MOFs with other materials,hybrid 2D MOF materials can be created.These hybrids,with their enhanced stability and conductivity,can be directly utilized as active materials in lithium batteries.In the present review,we categorize 2D MOF-based materials into three distinct groups:pristine 2D MOFs,2D MOFderived materials,and 2D MOF hybrid materials.The synthesis methods for each group,along with their specific applications as electrode materials in lithium-ion batteries,are discussed in detail.This comprehensive review provides insights into the potential of 2D MOFs while highlighting the opportunities and challenges that are present in this evolving field.

A review on anode materials for lithium/sodium-ion batteries

Since lithium-ion batteries(LIBs) have been substantially researched in recent years, they now possess exceptional energy and power densities, making them the most suited energy storage technology for use in developed and developing industries like stationary storage and electric cars, etc. Concerns about the cost and availability of lithium have prompted research into alternatives, such as sodium-ion batteries(SIBs), which use sodium instead of lithium as the charge carrier. This is especially relevant for stationary applications, where the size and weight of battery are less important. The working efficiency and capacity of these batteries are mainly dependent on the anode, cathode, and electrolyte. The anode,which is one of these components, is by far the most important part of the rechargeable battery.Because of its characteristics and its structure, the anode has a tremendous impact on the overall performance of the battery as a whole. Keeping the above in view, in this review we critically reviewed the different types of anodes and their performances studied to date in LIBs and SIBs. The review article is divided into three main sections, namely:(i) intercalation reaction-based anode materials;(ii) alloying reaction-based anode materials;and(iii) conversion reaction-based anode materials, which are further classified into a number of subsections based on the type of material used. In each main section, we have discussed the merits and challenges faced by their particular system. Afterward, a brief summary of the review has been discussed. Finally, the road ahead for better application of Li/Na-ion batteries is discussed, which seems to mainly depend on exploring the innovative materials as anode and on the inoperando characterization of the existing materials for making them more capable in terms of application in rechargeable batteries.

Advances in the structure design of substrate materials for zinc anode of aqueous zinc ion batteries

Aqueous zinc ion batteries(AZIBs) demonstrate tremendous competitiveness and application prospects because of their abundant resources,low cost, high safety, and environmental friendliness. Although the advanced electrochemical energy storage systems based on zinc ion batteries have been greatly developed, many severe problems associated with Zn anode impede its practical application, such as the dendrite formation,hydrogen evolution, corrosion and passivation phenomenon. To address these drawbacks, electrolytes, separators, zinc alloys, interfacial modification and structural design of Zn anode have been employed at present by scientists. Among them, the structural design for zinc anode is relatively mature, which is generally believed to enhance the electroactive surface area of zinc anode, reduce local current density, and promote the uniform distribution of zinc ions on the surface of anode. In order to explore new research directions, it is crucial to systematically summarize the structural design of anode materials. Herein, this review focuses on the challenges in Zn anode, modification strategies and the three-dimensional(3D) structure design of substrate materials for Zn anode including carbon substrate materials, metal substrate materials and other substrate materials. Finally, future directions and perspectives about the Zn anode are presented for developing high-performance AZIBs.

Carbon-coated ZnO Nanocomposite Microspheres as Anode Materials for Lithium-ion Batteries

The carbon-coated ZnO nanospheres materials have been synthesized via a simple hydrothermal method.The effect of carbon content on the microstructure,morphology and electrochemical performance of the materials was investigated by XRD,Raman spectroscopy,transmission electron microscopy,scanning electron microscopy and electrochemical techniques.Research results show that the spherical ZnO/C material with a carbon cladding content of 10%is very homogeneous and approximately 200 nm in size.The electrochemical performances of the ZnO/C nanospheres as an anode materials are examines.The ZnO/C exhibits better stability than pure ZnO,excellent lithium storage properties as well as improved circulation performance.The Coulomb efficiency of the ZnO/C with 10%carbon coated content reaches 98%.The improvement of electrochemical performance can be attributed to the carbon layer on the ZnO surface.The large volume change of ZnO during the charge-discharge process can be effectively relieved.

Two-dimensional dumbbell silicene as a promising anode material for(Li/Na/K)-ion batteries

Rechargeable ion batteries require anode materials with excellent performance,presenting a key challenge for researchers.This paper explores the potential of using two-dimensional dumbbell silicene as an anode material for alkali metal ion batteries through density functional theory(DFT)calculations.Our findings demonstrate that alkali metal ions have negative adsorption energies on dumbbell silicene,and the energy barriers for Li/Na/K ion diffusion are as low as0.032 e V/0.055 e V/0.21 e V,indicating that metal ions can easily diffuse across the entire surface of dumbbell silicene.Additionally,the average open circuit voltages of dumbbell silicene as anode for Li-ion,Na-ion,and K-ion batteries are 0.42 V,0.41 V,and 0.60 V,respectively,with corresponding storage capacities of 716 m Ah/g,622 m Ah/g,and 716 m Ah/g.These results suggest that dumbbell silicene is an ideal anode material for Li-ion,Na-ion,and K-ion batteries,with high capacity,low open circuit voltage,and high ion diffusion kinetics.Moreover,our calculations show that the theoretical capacities obtained using DFT-D2 are higher than those obtained using DFT-D3,providing a valuable reference for subsequent theoretical calculations.

The Microparticles SiOx Loaded on PAN-C Nanofiber as Three-Dimensional Anode Material for High-Performance Lithium-Ion Batteries

Three-dimensional C/SiOx nanofiber anode was prepared by polydimethylsiloxane(PDMS)and polyacrylonitrile(PAN)as precursors via electrospinning and freeze-drying successfully.In contrast to conventional carbon cover-ing Si-based anode materials,the C/SiOx structure is made up of PAN-C,a 3D carbon substance,and SiOx load-ing steadily on PAN-C.The PAN carbon nanofibers and loaded SiOx from pyrolyzed PDMS give increased conductivity and a stable complex structure.When employed as lithium-ion batteries(LIBs)anode materials,C/SiOx-1%composites were discovered to have an extremely high lithium storage capacity and good cycle per-formance.At a current density of 100 mA/g,its reversible capacity remained at 761 mA/h after 50 charge-dis-charge cycles and at 670 mA/h after 200 cycles.The C/SiOx-1%composite aerogel is a particularly intriguing anode candidate for high-performance LIBs due to these appealing qualities.

Pressure-Induced Pre-Lithiation Enables High-Performing Si Anodes in All-Solid-State Batteries

A commentary on pressure-induced pre-lithiation towards Si anodes in allsolid-state Li-ion batteries(ASSLIBs)using sulfide electrolytes(SEs)is presented.First,feasible pre-lithiation technologies for Si anodes in SE-based ASSLIBs especially the significant pressure-induced pre-lithiation strategies are briefly reviewed.Then,a recent achievement by Meng et al.in this field is elaborated in detail.Finally,the significance of Meng’s work is discussed.

Recent Progress in Improving Rate Performance of Cellulose-Derived Carbon Materials for Sodium-Ion Batteries

Cellulose-derived carbon is regarded as one of the most promising candidates for high-performance anode materials in sodium-ion batteries;however,its poor rate performance at higher current density remains a challenge to achieve high power density sodium-ion batteries.The present review comprehensively elucidates the structural characteristics of cellulose-based materials and cellulose-derived carbon materials,explores the limitations in enhancing rate performance arising from ion diffusion and electronic transfer at the level of cellulose-derived carbon materials,and proposes corresponding strategies to improve rate performance targeted at various precursors of cellulose-based materials.This review also presents an update on recent progress in cellulose-based materials and cellulose-derived carbon materials,with particular focuses on their molecular,crystalline,and aggregation structures.Furthermore,the relationship between storage sodium and rate performance the carbon materials is elucidated through theoretical calculations and characterization analyses.Finally,future perspectives regarding challenges and opportunities in the research field of cellulose-derived carbon anodes are briefly highlighted.

Si-Based Anode Materials for Li-Ion Batteries:A Mini Review

Si has been considered as one of the most attractive anode materials for Li-ion batteries(LIBs) because of its high gravimetric and volumetric capacity. Importantly, it is also abundant, cheap, and environmentally benign. In this review, we summarized the recent progress in developments of Si anode materials. First, the electrochemical reaction and failure are outlined, and then, we summarized various methods for improving the battery performance, including those of nanostructuring, alloying, forming hierarchic structures, and using suitable binders. We hope that this review can be of benefit to more intensive investigation of Si-based anode materials.

Controlled synthesis of nanosized Si by magnesiothermic reduction from diatomite as anode material for Li-ion batteries

Li-ion batteries(LIBs)have demonstrated great promise in electric vehicles and hybrid electric vehicles.However,commercial graphite materials,the current predominant anodes in LIBs,have a low theoretical capacity of only 372 mAh·g?1,which cannot meet the everincreasing demand of LIBs for high energy density.Nanoscale Si is considered an ideal form of Si for the fabrication of LIB anodes as Si–C composites.Synthesis of nanoscale Si in a facile,cost-effective way,however,still poses a great challenge.In this work,nanoscale Si was prepared by a controlled magnesiothermic reaction using diatomite as the Si source.It was found that the nanoscale Si prepared under optimized conditions(800°C,10 h)can deliver a high initial specific capacity(3053 mAh·g?1 on discharge,2519 mAh·g?1 on charge)with a high first coulombic efficiency(82.5%).When using sand-milled diatomite as a precursor,the obtained nanoscale Si exhibited a well-dispersed morphology and had a higher first coulombic efficiency(85.6%).The Si–C(Si:graphite=1:7 in weight)composite using Si from the sand-milled diatomite demonstrated a high specific capacity(over 700 mAh·g?1 at 100 mA·g?1),good rate capability(587 mAh·g?1 at 500 mA·g?1),and a long cycle life(480 mAh·g?1 after 200 cycles at 500 mA·g?1).This work gives a facile method to synthesize nanoscale Si with both high capacity and high first coulombic efficiency.

CoFe_2O_4-Graphene Nanocomposites Synthesized through An Ultrasonic Method with Enhanced Performances as Anode Materials for Li-ion Batteries

Co Fe2O4-graphene nanosheets(Co Fe2O4-GNSs) were synthesized through an ultrasonic method, and their electrochemical performances as Li-ion battery electrode were improved by annealing processes. The nanocomposites obtained at 350 °C maintained a high specific capacity of 1,257 m Ah g-1even after 200 cycles at 0.1 A g-1. Furthermore,the obtained materials also have better rate capability, and it can be maintained to 696, 495, 308, and 254 m Ah g-1at 1, 2,5, and 10 A g-1, respectively. The enhancements realized in the reversible capacity and cyclic stability can be attributed to the good improvement in the electrical conductivity achieved by annealing at appropriate temperature, and the electrochemical nature of Co Fe2O4 and GNSs during discharge–charge processes.

All boron-based 2D material as anode material in Li-ion batteries

To design the high-energy-density Li-ion batteries, the anode materials with high specific capacity haveattracted much attention. In this work, we adopt the first principles calculations to investigate the pos-sibility of a new two dimensional boron material, named Be, as anode material for Li-ion batteries. Thecalculated results show that the maximum theoretical specific capacity of Bc is 1653mAh g-1 （LiBl.s）.Additionally, the energy barriers of Li ion and Li vacancy diffusion are 330 meV and 110 meV, respec-tively, which imply fast charge and discharge ability for B6 as an anode material. The theoretical findingsreported in this work suggest that BG is a potential candidate as anode material of high-energy-density Li-ion batteries.

Bi nanoparticles in situ encapsulated by carbon film as high-performance anode materials for Li-ion batteries

Bismuth (Bi) has indeed inspired great interests in lithium-ion batteries (LIBs) due to the high capacity,but was still limited by the low electrical conductivity and large volume variation.Herein,a composite material based on Bi nanoparticles in situ encapsulated by carbon film (Bi@CF) is prepared successfully through a facile metal–organic framework (MOF)-engaged approach.As anode materials for LIBs,the Bi@CF composites achieved high reversible capacities of 705 and 538 mAh g^(-1)at 0.2 and 0.5 A g^(-1) after200 cycles,and long cycling performance with a stable capacity of 306 mAh g^(-1)at 1.0 A g^(-1) even after 900 cycles.In situ X-ray diffraction (XRD) measurements clearly revealed the conversion between Bi and Li_(3)Bi during the alloying/dealloying process,confirming the good electrochemical reversibility of Bi@CF for Li-storage.The reaction kinetics of this Bi@CF composite was further studied by galvanostatic intermittent titration technique (GITT).This work may provide an inspiration for the elaborate design and facile preparation of alloy-type anode materials for high-performance rechargeable batteries.

Nanoporous SiO_x coated amorphous silicon anode material with robust mechanical behavior for high-performance rechargeable Li-ion batteries

Silicon is a promising anode material for rechargeable Li-ion battery (LIB) due to its high energy density and relatively low operating voltage. However, silicon based electrodes suffer from rapid capacity degradation during electrochemical cycling. The capacity decay is predominantly caused by (i) cracking due to large volume variations during lithium insertion/extraction and (ii) surface degradation due to excessive solid electrolyte interface (SEI) formation. In this work, we demonstrate that coating of a-Si thin film with a Li-active, nanoporous SiOx layer can result in exceptional electrochemical performance in Li-ion battery. The SiOx layer provides improved cracking resistance to the thin film and prevent the active material loss due to excessive SEI formation, benefiting the electrode cycling stability. Half-cell experiments using this anode material show an initial reversible capacity of 2173 mAh g^-1 with an excellent coulombic efficiency of 90.9%. Furthermore, the electrode shows remarkable capacity retention of ~97% after 100 cycles at C/2 charging rate. The proposed anode architecture is free from Liinactive binders and conductive additives and provides mechanical stability during the charge/discharge process.