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.

Access to advanced sodium-ion batteries by presodiation:Principles and applications

Sodium-ion batteries(SIBs)are expected to offer affordability and high energy density for large-scale energy storage system.However,the commercial application of SIBs is hurdled by low initial coulombic efficiency(ICE),continuous Na loss during long-term operation,and low sodium-content of cathode materials.In this scenario,presodiation strategy by introducing an external sodium reservoir has been rationally proposed,which could supplement additional sodium ions into the system and thereby markedly improve both the cycling performance and energy density of SIBs.In this review,the significance of presodiation is initially introduced,followed by comprehensive interpretation on technological properties,underlying principles,and associated approaches,as well as our perspectives on present inferiorities and future research directions.Overall,this contribution outlines a distinct pathway towards the presodiation methodology,of significance but still in its nascent phase,which may inspire the targeted guidelines to explore new chemistry in this field.

The safety aspect of sodium ion batteries for practical applications

Sodium-ion batteries(SIBs)with advantages of abundant resource and low cost have emerged as promising candidates for the next-generation energy storage systems.However,safety issues existing in electrolytes,anodes,and cathodes bring about frequent accidents regarding battery fires and explosions and impede the development of high-performance SIBs.Therefore,safety analysis and high-safety battery design have become prerequisites for the development of advanced energy storage systems.The reported reviews that only focus on a specific issue are difficult to provide overall guidance for building high-safety SIBs.To overcome the limitation,this review summarizes the recent research progress from the perspective of key components of SIBs for the first time and evaluates the characteristics of various improvement strategies.By orderly analyzing the root causes of safety problems associated with different components in SIBs(including electrolytes,anodes,and cathodes),corresponding improvement strategies for each component were discussed systematically.In addition,some noteworthy points and perspectives including the chain reaction between security issues and the selection of improvement strategies tailored to different needs have also been proposed.In brief,this review is designed to deepen our understanding of the SIBs safety issues and provide guidance and assistance for designing high-safety SIBs.

A Molecular-Sieving Interphase Towards Low-Concentrated Aqueous Sodium-Ion Batteries

Aqueous sodium-ion batteries are known for poor rechargeability because of the competitive water decomposition reactions and the high electrode solubility.Improvements have been reported by saltconcentrated and organic-hybridized electrolyte designs,however,at the expense of cost and safety.Here,we report the prolonged cycling of ASIBs in routine dilute electrolytes by employing artificial electrode coatings consisting of NaX zeolite and NaOH-neutralized perfluorinated sulfonic polymer.The as-formed composite interphase exhibits a molecularsieving effect jointly played by zeolite channels and size-shrunken ionic domains in the polymer matrix,which enables high rejection of hydrated Na^(+)ions while allowing fast dehydrated Na^(+)permeance.Applying this coating to electrode surfaces expands the electrochemical window of a practically feasible 2 mol kg^(-1) sodium trifluoromethanesulfonate aqueous electrolyte to 2.70 V and affords Na_(2)MnFe(CN)_(6)//NaTi_(2)(PO_(4))_(3) full cells with an unprecedented cycling stability of 94.9%capacity retention after 200 cycles at 1 C.Combined with emerging electrolyte modifications,this molecular-sieving interphase brings amplified benefits in long-term operation of ASIBs.

Experimental and computational optimization of Prussian blue analogues as high-performance cathodes for sodium-ion batteries:A review

In this review,we discuss the electrochemical properties of Prussian blue(PB)for Na^(+)storage by combining structural engineering and electrolyte modifications.We integrated experimental data and density functional theory(DFT)in sodium-ion battery(SIB)research to refine the atomic arrangements and crystal lattices and introduce substitutions and dopants.These changes affect the lattice stability,intercalation,electronic and ionic conductivities,and electrochemical performance.We unraveled the intricate structure-electrochemical behavior relationship by combining experimental data with computational models,including first-principles calculations.This holistic approach identified techniques for optimizing PB and Prussian blue analog(PBA)structu ral properties for SIBs.We also discuss the tuning of electrolytes by systematically adjusting their composition,concentration,and additives using a combination of molecular dynamics(MD)simulations and DFT computations.Our review offers a comprehensive assessment of strategies for enhancing the electrochemical properties of PB and PBAs through structural engineering and electrolyte modifications,combining experimental insights with advanced computational simulations,and paving the way for next-generation energy storage systems.

Extending the solid solution range of sodium ferric pyrophosphate:Off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)as a novel cathode for sodium‐ion batteries

Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.

Hetero-interfacial nickel nitride/vanadium oxynitride porous nanosheets as trifunctional electrodes for HER,OER and sodium ion batteries

The development of single electrode with multifunctional purposes for electrochemical devices remains a symbolic challenge in recent technology.This work explores interfacially-rich transition metal nitride hybrid that consist of nickel nitride and vanadium oxynitride(VO_(0.26)N_(0.52))on robust carbon fiber(denoted CF/Ni_(3)N/VON)as trifunctional electrode for hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and sodium ion batteries(SIBs).The as-prepared CF/Ni_(3)N/VON exhibits low HER overpotential of 48 m V@10 m A cm^(-2),OER overpotential of 287 m V@10 m A cm^(-2),and sodium-ion anode storage reversible capacity of 555 m A h g^(-1)@0.2 C.Theoretical analyses reveal that the Ni_(3)N effectively facilitates hydrogen desorption for HER,increases the electrical conductivity for OER,and promotes the Na-ion storage intercalation process,while the VON substantially elevates the water dissociation kinetics for HER,accelerates the adsorption of OH*intermediate for OER and enhances the Na-ion surface adsorption storage process.Owing to the excellent HER and OER performances of the CF/Ni_(3)N/VON electrode,an overall water splitting device denoted as CF/Ni_(3)N/VON//CF/Ni_(3)N/VON was not only assembled showing an operating voltage of 1.63 V at current density of 10 m A cm^(-2)but was also successfully self-powered by the assembled CF/Ni_(3)N/VON//CF/Na_(3)V_(2)(PO_(4))_(3) flexible sodium ion battery.This work will contribute to the development of efficient and cost-effective flexible integrated electrochemical energy devices.

One-step electrochemical in-situ Li doping and LiF coating enable ultra-stable cathode for sodium ion batteries

Despite of the higher energy density and inexpensive characteristics,commercialization of layered oxide cathodes for sodium ion batteries(SIBs)is limited due to the lack of structural stability at the high voltage.Herein,the one-step electrochemical in-situ Li doping and LiF coating are successfully achieved to obtain an advanced Na0.79Lix[Li_(0.13)Ni_(0.20)Mn_(0.67)]O_(2)@LiF(NaLi-LNM@LiF)cathode with superlattice structure.The results demonstrate that the Li^(+)doped into the alkali metal layer by electrochemical cycling act as"pillars"in the form of Li-Li dimers to stabilize the layered structure.The supplementation of Li to the superlattice structure inhibits the dissolution of transition metal ions and lattice mismatch.Furthermore,the in-situ LiF coating restrains side reactions,reduces surface cracks,and greatly improves the cycling stability.The electrochemical in-situ modification strategy significantly enhances the electrochemical performance of the half-cell.The NaLi-LNM@LiF exhibits high reversible specific capacity(170.6 m A h g^(-1)at 0.05 C),outstanding capacity retention(92.65%after 200 cycles at 0.5 C)and excellent rate performance(80 mA h g^(-1)at 7 C)in a wide voltage range of 1.5-4.5 V.This novel method of in-situ modification by electrochemical process will provide a guidance for the rational design of cathode materials for SIBs.

A general synthesis of inorganic nanotubes as high-rate anode materials of sodium ion batteries

Ino rganic tubular materials have an exceptionally wide range of applications,yet developing a simple and universal method to controllably synthesize them remains challenging.In this work,we report a vaporphase-etching hard-template method that can directly fabricate tubes on various thermally stable oxide and sulfide materials.This synthesis method features the introduction of a vapor-phase-etching process to greatly simplify the steps involved in preparing tubular materials and avoids complicated postprocessing procedures.Furthermore,the in-situ heating transmission electron microscopy(TEM)technique is used to observe the dynamic formation process of TiO_(2-x) tubes,indicating that the removal process of the Sb2S3 templates first experienced the Rayleigh instability,then vapor-phase-etching process.When used as an anode for sodium ion batteries,the TiO_(2-x) tube exhibits excellent rate performance of134.6 mA h g^(-1) at the high current density of 10 A g^(-1) and long-term cycling over 7000 cycles.Moreover,the full cell demonstrates excellent cycling performance with capacity retention of 98%after 1000 cycles,indicating that it is a promising anode material for batteries.This method can be expanded to the design and synthesis of other thermally-stable tubular materials such as ZnS,MoS_(2),and SiO_(2).

Clarification of underneath capacity loss for O3-type Ni, co free layered cathodes at high voltage for sodium ion batteries

Earth abundant O3-type NaFe_(0.5)Mn_(0.5)O_(2)layered oxide is regarded as one of the most promising cathodes for sodium ion batteries due to its low cost and high energy density.However,its poor structural stability and cycle life strongly impede the practical application.Herein,the dynamic phase evolution as well as charge compensation mechanism of O3-type NaFe_(0.5)Mn_(0.5)O_(2)cathode during sodiation/desodiation are revealed by a systemic study with operando X-ray diffraction and X-ray absorption spectroscopy,high resolution neutron powder diffraction and neutron pair distribution functions.The layered structure experiences a phase transition of O3→P3→OP2→ramsdellite during the desodiation,and a new O3’phase is observed at the end of the discharge state(1.5 V).The density functional theory(DFT)calculations and nPDF results suggest that depletion of Na^(+)ions induces the movement of Fe into Na layer resulting the formation of an inert ramsdellite phase thus causing the loss of capacity and structural integrity.Meanwhile,the operando XAS clarified the voltage regions for active Mn^(3+)/Mn^(4+)and Fe^(3+)/Fe^(4+)redox couples.This work points out the universal underneath problem for Fe-based layered oxide cathodes when cycled at high voltage and highlights the importance to suppress Fe migration regarding the design of high energy O3-type cathodes for sodium ion batteries.

Sodium-Coordinated Polymeric Phthalocyanines as Stable High-Capacity Organic Anodes for Sodium-Ion Batteries

Sodium-ion batteries(SIBs)have attracted considerable interest as an alternative to lithium-ion batteries owing to their similar electrochemical performance and superior long-term cycle stability.Organic materials are regarded as promising anode materials for constructing SIBs with high capacity and good retention.However,utilization of organic materials is rather limited by their low energy density and poor stability at high current densities.To overcome these limitations,we utilized a novel polymeric disodium phthalocyanines(pNaPc)as SIB anodes to provide stable coordination sites for Na ions as well as to enhance the stability at high current density.By varying the linker type during a one-pot cyclization and polymerization process,two pNaPc anodes with O-(O-pNaPc)and S-linkers(S-pNaPc)were prepared,and their structural and electrochemical properties were investigated.The O-pNaPc binds Na ions with a lower binding energy compared with S-pNaPc,which leads to more facile Na-ion coordination/dissociation when engaged as SIB anode.The use of O-pNaPc significantly improves the redox kinetics and cycle stability and allows the fabrication of a full cell against Na_(3)V_(2)(PO_(4))_(2)F_(3)/C cathode,which demonstrates its practical application with high energy density(288 Wh kg^(-1))and high power density(149 W kg^(-1)).

Phase-engineering modulation of Mn-based oxide cathode for constructing super-stable sodium storage

The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by the sluggish Na^(+)kinetics and the phase transitions upon cycling.Herein,we establish the thermodynamically stable phase diagram of various Mn-based oxide composites precisely controlled by sodium content tailoring strategy coupling with co-doping and solid-state reaction.The chemical environment of the P2/P'3 and P2/P3 biphasic composites indicate that the charge compensation mechanism stems from the cooperative contribution of anions and cations.Benefiting from the no phase transition to scavenge the structure strain,P2/P'3 electrode can deliver long cycling stability(capacity retention of 73.8%after 1000 cycles at 10 C)and outstanding rate properties(the discharge capacity of 84.08 mA h g^(-1)at 20 C)than P2/P3 electrode.Furthermore,the DFT calculation demonstrates that the introducing novel P'3 phase can significantly regulate the Na^(+)reaction dynamics and modify the local electron configuration of Mn.The effective phase engineering can provide a reference for designing other high-performance electrode materials for Na-ion batteries.

Delving into the dissimilarities in electrochemical performance and underlying mechanisms for sodium and potassium ion storage in N-doped carbon-encapsulated metallic Cu_(2)Se nanocubes

The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical performance.Herein,metallic Cu_(2)Se encapsulated with N-doped carbon(Cu_(2)Se@NC)was prepared using Cu_(2)O nanocubes as templates through a combination of dopamine polymerization and hightemperature selenization.The unique nanocubic structure and uniform N-doped carbon coating could shorten the ion transport distance,accelerate electron/charge diffusion,and suppress volume variation,ultimately ensuring Cu_(2)Se@NC with excellent electrochemical performance in sodium ion batteries(SIBs)and potassium ion batteries(PIBs).The composite exhibited excellent rate performance(187.7 mA h g^(-1)at 50 A g^(-1)in SIBs and 179.4 mA h g^(-1)at 5 A g^(-1)in PIBs)and cyclic stability(246,8 mA h g^(-1)at 10 A g^(-1)in SIBs over 2500 cycles).The reaction mechanism of intercalation combined with conversion in both SIBs and PIBs was disclosed by in situ X-ray diffraction(XRD)and ex situ transmission electron microscope(TEM).In particular,the final products in PIBs of K_(2)Se and K_(2)Se_(3)species were determined after discharging,which is different from that in SIBs with the final species of Na_(2)Se.The density functional theory calculation showed that carbon induces strong coupling and charge interactions with Cu_(2)Se,leading to the introduction of built-in electric field on heterojunction to improve electron mobility.Significantly,the theoretical calculations discovered that the underlying cause for the relatively superior rate capability in SIBs to that in PIBs is the agile Na~+diffusion with low energy barrier and moderate adsorption energy.These findings offer theoretical support for in-depth understanding of the performance differences of Cu-based materials in different ion storage systems.

Innovative Mn_(3-x)O_(4-y)@NCA design:Leveraging Mn/O vacancies and amorphous architecture for enhanced sodium-ion storage

Manganese-based oxide electrode materials suffer from severe Jahn-Teller(J-T)distortion,leading to severe cycle instability in sodium ion storage.However,it is difficult to adjust the electron at d orbitals exactly to a low spin state to eliminate orbital degeneracy and suppress J-T distortion fundamentally.This article constructed concentration-controllable Mn/O coupled vacancy and amorphous network in Mn_(3)O_(4) and coated it with nitrogen-doped carbon aerogel(Mn_(3-x)O_(4-y)@NCA).The existence of Mn/O vacancies has been confirmed by scanning transmission electron microscopy(STEM)and positron annihilation lifetime spectroscopy(PALS).Atomic absorption spectroscopy(AAS)and X-ray photoelectron spectroscopy(XPS)determine the most optimal ratio of Mn/O vacancies for sodium ion storage is 1:2.Density functional theory(DFT)calculations prove that Mn/O coupled vacancies with the ratio of 1:2could exactly induce a low spin states and a d~4 electron configuration of Mn,suppressing the J-T distortion successfully.The abundant amorphous regions can shorten the transport distance of sodium ions,increase the electrochemically active sites and improve the pseudocapacitance response.From the synergetic effect of Mn/O coupled vacancies and amorphous regions,Mn_(3-x)O_(4-y)@NCA exhibits an energy density of 37.5 W h kg^(-1)and an ultra-high power density of 563 W kg^(-1)in an asymmetric supercapacitor.In sodium-ion batteries,it demonstrates high reversible capacity and exceptional cycling stability.This research presents a new method to improve the Na^(+)storage performance in manganese-based oxide,which is expected to be generalized to other structural distortion.

Bimetallic selenide heterostructure with directional built-in electricfield confined in N-doped carbon nanofibers for superior sodium storage with ultralong lifespan

Constructing heterostructure is considered as an effective strategy to address the sluggish electronic and ionic kinetics of anode materials for sodium ion batteries(SIBs).However,realizing the orientated growth and uniform distribution of the heterostructure is still a great challenge.Herein,the regulated novel CoSe_(2)/NiSe_(2)heterostructure confined in N-doped carbon nanofibers(CoSe_(2)/NiSe_(2)@N-C)are prepared by using Co/Ni-ZIF template,in which,the CoSe_(2)/NiSe_(2)heterostructures realize uniform distribution on a micro level.Benefiting from the unique heterostructure and N-doped carbon nanofibers,the CoSe_(2)/NiSe_(2)@N-C deliveries superior rate capability and durable cycle lifespan with a reversible capacity of 400.5 mA h g^(-1)after 5000 cycles at 2 A g^(-1).The Na-ion full battery with CoSe_(2)/NiSe_(2)@N-C anode and layered oxide cathode displays a remarkable energy density of 563 W h kg^(-1)with 241.1 W kg^(-1)at 0.1 A g^(-1).The theoretical calculations disclose that the periodic and directional built-in electric-field along with the heterointerfaces of CoSe_(2)/NiSe_(2)@N-C can accelerate electrochemical reaction kinetics.The in(ex)situ experimental measurements reveal the reversible conversion reaction and stable structure of CoSe_(2)/NiSe_(2)@N-C during Na+insertion/extraction.The study highlights the potential ability of precisely controlled heterostructure to stimulate the electrochemical performances of advanced anode for SIBs.

Solid-state NMR study on sodium intercalation at low voltage window for Na_(3)V_(2)(PO_(4))_(3) as an anode

In-situ XRD,^(31)P NMR and ^(23)Na NMR were used to analyze the interaction behavior of Na_(3)V_(2)(PO_(4))_(3) at low voltage,and then a new intercalation model was proposed.During the transition from Na_(3)V_(2)(PO_(4))_(3) to Na_(4)V_(2)(PO_(4))_(3),Na ions insert into M1,M2 and M3 sites simultaneously.Afterwards,during the transition of Na_(4)V_(2)(PO_(4))_(3)to Na_(5)V_(2)(PO_(4))_(3),Na ions mainly insert into M3 site.

Synthesis and Conductivity Characterization of Anti-Perovskite Na3OX Solid Electrolytes for All Solid Na-Ion Batteries

Solid electrolytes for all solid sodium-ion batteries have been attracting much attention as an alternative energy storage system, which have the advantage of being extremely safe because it can be charged quickly and is nonflammable. We have synthesized anti-perovskite type Na3OX (X = Br, and I) electrolytes with high purity, by reactions of halogen mixtures with sodium oxides. After mixing, it was filled in an alumina crucible and heated for 6 hours at 330°C. It was confirmed that a large crystal strain was introduced by eutectication, which might reduce the activation energy of Na ion conduction and lead to an improvement of the conductivity. A relatively higher ionic conductivity of σ = 1.55 × 10-7 S/cm at 60°C has been obtained for Na3OBr0.6I0.4, which is about three orders higher than that in literature. A different ratio of X (X = Br, I) ions was added into sodium oxide to make the Na3OX crystal. The influence of strain introduction on optimizing the bottleneck and improving the conductivity was discussed.

Hard carbon derived from cellulose as anode for sodium ion batteries:Dependence of electrochemical properties on structure

Cellulose, the most abundant organic polymer on Earth, is a sustainable source of carbon to use as a negative electrode for sodium ion batteries. Here, hard carbons(HC) prepared by cellulose pyrolysis were investigated with varying pyrolysis temperature from 700 °C to 1600 °C. Characterisation methods such as Small Angle X-ray Scattering(SAXS) measurements and N2adsorption were performed to analyse porosity differences between the samples. The graphene sheet arrangements were observed by transmission electron microscopy(TEM): an ordering of the graphene sheets is observed at temperatures above 1150 °C and small crystalline domains appear over 1400 °C. As the graphene sheets start to align, the BET surface area decreases and the micropore size increases. To correlate hard carbon structures and electrochemical performances, different tests in Na//HC cells with 1 M NaPF6ethylene carbonate/dimethyl carbonate(EC/DMC) were performed. Samples pyrolysed from 1300 °C to 1600 °C showed a 300 m Ah/g reversible capacity at C/10 rate(where C = 372 mA/g) with an excellent stability in cycling and a very good initial Coulombic efficiency of up to 84%. Furthermore, hard carbons showed an excellent rate capability where sodium extraction rate varies from C/10 to 5C. At 5C more than 80% of reversible capacity remains stable for hard carbons synthesized from 1000 °C to 1600 °C.

SnS_2@C Hollow Nanospheres with Robust Structural Stability as High?Performance Anodes for Sodium Ion Batteries

Constructing unique and highly stable structures with plenty of electroactive sites in sodium storage materials is a key factor for achieving improved electrochemical properties through favorable sodium ion di usion kinetics. An SnS_2@carbon hollow nanospheres(SnS_2@C) has been designed and fabricated via a facile solvothermal route, followed by an annealing treatment. The SnS_2@C hybrid possesses an ideal hollow structure, rich active sites, a large electrode/electrolyte interface, a shortened ion transport pathway, and, importantly, a bu er space for volume change, generated from the repeated insertion/extraction of sodium ions. These merits lead to the significant reinforcement of structural integrity during electrochemical reactions and the improvement in sodium storage properties, with a high specific reversible capacity of 626.8 mAh g^(-1) after 200 cycles at a current density of 0.2 A g^(-1) and superior high-rate performance(304.4 mAh g^(-1) at 5 A g^(-1)).

Microwave-Assisted Synthesis of NiCo_2O_4 Double-Shelled Hollow Spheres for High-Performance Sodium Ion Batteries

The ternary transitional metal oxide NiCo_2O_4 is a promising anode material for sodium ion batteries due to its high theoretical capacity and superior electrical conductivity. However, its sodium storage capability is severely limited by the sluggish sodiation/desodiation reaction kinetics. Herein, NiCo_2O_4 double-shelled hollow spheres were synthesized via a microwave-assisted, fast solvothermal synthetic procedure in a mixture of isopropanol and glycerol, followed by annealing. Isopropanol played a vital role in the precipitation of nickel and cobalt,and the shrinkage of the glycerol quasi-emulsion under heat treatment was responsible for the formation of the double-shelled nanostructure. The as-synthesized productwas tested as an anode material in a sodium ion battery,was found to exhibit a high reversible specific capacity of 511 m Ahg^(-1) at 100 m Ag^(-1), and deliver high capacity retention after 100 cycles.