Natural Lignin:A Sustainable and Cost-Effective Electrode Material for High-Temperature Na-Ion Battery

Rechargeable sodium-ion batteries usually suffer from accelerated electrode destruction at high temperatures and high synthesis costs of electrode materials.Therefore,it is highly desirable to explore novel organic electrodes considering their cost-effectiveness and large adaptability to volume changes.Herein,natural biomass,pristine lignin,is employed as the sodium-ion battery anodes,and their sodium storage performance is investigated at room temperature and 60℃.The lignin anodes exhibit excellent high-temperature sodium-ion battery performance.This mainly results from the generation of abundant reactive sites(C=O)due to the high temperature-induced homogeneous cleavage of the C_(β)-O bond in the lignin macromolecule.This work can inspire researchers to explore other natural organic materials for large-scale applications and high-value utilization in advanced energy storage devices.

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.

Research on the impact of high-temperature aging on the thermal safety of lithium-ion batteries

Understanding the thermal safety evolution of lithium-ion batteries during high-temperature usage conditions bears significant implications for enhancing the safety management of aging batteries.This work investigates the thermal safety evolution mechanism of lithium-ion batteries during high-temperature aging.Similarities arise in the thermal safety evolution and degradation mechanisms for lithium-ion batteries undergoing cyclic aging and calendar aging.Employing multi-angle characterization analysis,the intricate mechanism governing the thermal safety evolution of lithium-ion batteries during high-temperature aging is clarified.Specifically,lithium plating serves as the pivotal factor contributing to the reduction in the self-heating initial temperature.Additionally,the crystal structure of the cathode induced by the dissolution of transition metals and the reductive gas generated during aging attacking the crystal structure of the cathode lead to a decrease in thermal runaway triggering temperature.Furthermore,the loss of active materials and active lithium during aging contributes to a decline in both the maximum temperature and the maximum temperature rise rate,ultimately indicating a decrease in the thermal hazards of aging batteries.

The chance of sodium titanate anode for the practical sodium-ion batteries

Supporting sustainable green energy systems,there is a big demand gap for grid energy storage.Sodiumion storage,especially sodium-ion batteries(SIBs),have advanced significantly and are now emerging as a feasible alternative to the lithium-ion batteries equivalent in large-scale energy storage due to their natural abundance and prospective inexpensive cost.Among various anode materials of SIBs,beneficial properties,such as outstanding stability,great abundance,and environmental friendliness,make sodium titanates(NTOs),one of the most promising anode materials for the rechargeable SIBs.Nevertheless,there are still enormous challenges in application of NTO,owing to its low intrinsic electronic conductivity and collapse of structure.The research on NTOs is still in its infancy;there are few conclusive reviews about the specific function of various modification methods.Herein,we summarize the typical strategies of optimization and analysis the fine structures and fabrication methods of NTO anodes combined with the application of in situ characterization techniques.Our work provides effective guidance for promoting the continuous development,equipping NTOs in safety-critical systems,and lays a foundation for the development of NTO-anode materials in SIBs.

Defect-rich N/O-co-doped porous carbon frameworks as anodes for superior potassium and sodium-ion batteries

Carbon with its high electrical conductivity,excellent chemical stability,and structure ability is the most promising an-ode material for sodium and potassium ion batteries.We developed a defect-rich porous carbon framework(DRPCF)built with N/O-co-doped mesoporous nanosheets and containing many defects using porous g-C_(3)N_(4)(PCN)and dopamine(DA)as raw materials.We prepared samples with PCN/DA mass ratios of 1/1,2/1 and 3/1 and found that the one with a mass ratio of 2/1 and a carbonization temperature of 700℃ in an Ar atmosphere(DRPCF-2/1-700),had a large specific surface area with an enormous pore volume and a large number of N/O heteroatom active defect sites.Because of this,it had the best pseudocapacitive sodium and potassium ion stor-age performance.A half battery of Na//DRPCF-2/1-700 maintained a capacity of 328.2 mAh g^(-1) after being cycled at 1 A g^(-1) for 900 cycles,and a half battery of K//DRPC-2/1-700 maintained a capacity of 321.5 mAh g^(-1) after being cycled at 1 A g^(-1) for 1200 cycles.The rate capability and cycling stability achieved by DRPCF-2/1-700 outperforms most reported carbon materials.Finally,ex-situ Raman spectroscopy analysis result confirms that the filling and removing of K^(+)and Na^(+)from the electrochemically active defects are responsible for the high capacity,superior rate and cycling performance of the DRPCF-2/1-700 sample.

Fe_(3)O_(4)/Fe/FeS Tri-Heterojunction Node Spawning N-Carbon Nanotube Scaffold Structure for High-Performance Sodium-Ion Battery

The Fe-based anode of sodium-ion batteries attracts much attention due to the abundant source,low-cost,and high specific capacity.However,the low electron and ion transfer rate,poor structural stability,and shuttle effect of NaS_(2)intermediate restrain its further development.Herein,the Fe_(3)O_(4)/Fe/FeS tri-heterojunction node spawned N-carbon nanotube scaffold structure(FHNCS)was designed using the modified MIL-88B(Fe)as a template followed by catalytic growth and sulfidation process.During catalytic growth process,the reduced Fe monomers catalyze the growth of N-doped carbon nanotubes to connect the Fe_(3)O_(4)/Fe/FeS tri-heterojunction node,forming a 3D scaffold structure.Wherein the N-doped carbon promotes the transfer of electrons between Fe_(3)O_(4)/Fe/FeS particles,and the tri-heterojunction facilitates the diffusion of electrons at the interface,to organize a 3D conductive network.The unique scaffold structure provides more active sites and shortens the Na^(+)diffusion path.Meanwhile,the structure exhibits excellent mechanical stability to alleviate the volume expansion during circulation.Furthermore,the Fe in Fe_(3)O_(4)/Fe heterojunction can adjust the dband center of Fe in Fe_(3)O_(4)to enhance the adsorption between Fe_(3)O_(4)and Na2S intermediate,which restrains the shuttle effect.Therefore,the FHNCS demonstrates a high specific capacity of 436 mAh g^(-1)at 0.5 A g^(-1),84.7%and 73.4%of the initial capacities are maintained after 100 cycles at 0.5 A g^(-1)and 1000 cycles at 1.0 A g^(-1).We believe that this strategy gives an inspiration for constructing Fe-based anode with excellent rate capability and cycling stability.

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.

Metal-Organic Framework Enabling Poly(Vinylidene Fluoride)-Based Polymer Electrolyte for Dendrite-Free and Long-Lifespan Sodium Metal Batteries

Sodium dentrite formed by uneven plating/stripping can reduce the utilization of active sodium with poor cyclic stability and,more importantly,cause internal short circuit and lead to thermal runaway and fire.Therefore,sodium dendrites and their related problems seriously hinder the practical application of sodium metal batteries(SMBs).Herein,a design concept for the incorporation of metal-organic framework(MOF)in polymer matrix(polyvinylidene fluoride-hexafluoropropylene)is practiced to prepare a novel gel polymer electrolyte(PH@MOF polymer-based electrolyte[GPE])and thus to achieve high-performance SMBs.The addition of the MOF particles can not only reduce the movement hindrance of polymer chains to promote the transfer of Na^(+)but also anchor anions by virtue of their negative charge to reduce polarization during electrochemical reaction.A stable cycling performance with tiny overpotential for over 800 h at a current density of 5 mA cm^(-2)with areal capacity of 5 mA h cm^(-2)is achieved by symmetric cells based on the resulted GPE while the Na_(3)V_(2)O_(2)(PO_(4))_(2)F@rGO(NVOPF)|PH@MOF|Nacell also displays impressive specific cycling capacity(113.3 mA h g^(-1)at 1 C)and rate capability with considerable capacity retention.

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.

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.

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.

Interface issues and challenges for NASICON-based solid-state sodium-metal batteries

All-solid-state sodium(Na)-metal batteries(ASSSMBs)are considered promising candidates for large-scale energy storage systems due to their abundant sodium resources,unparalleled safety performance,and impressive energy density.Na superionic conductors(NASICONs)are among the best enablers of ASSSMBs in view of their high ionic conductivity,ease of synthesis,and excellent thermal stability and good electrochemical/chemical compatibility with common electrodes.However,challenges surrounding the NASICON/electrode interface,such as high interfacial resistance and dendrite formation,have hindered the development of practical ASSSMBs based on NASICONs.This review starts with an explicit summary of the interface problems between the metallic Na anode and NASICON arising from mechanical,chemical,and electrochemical aspects(i.e.,poor interface contact,insulating side-reaction products,and irregular dendrite growth).Subsequently,we systematically analyze and logically categorize modification strategies for addressing anode interface problems and provide a comprehensive discussion on the underlying enhancement mechanisms.As such,we identify underlying and universal interface enhancement mechanisms by comparatively studying various modification strategies.Furthermore,we briefly summarize the challenges in the cathode/electrolyte interface and early-stage research efforts in constructing stable cathode/electrolyte interface and fabricating high-performance composite cathodes.Finally,key suggestions and future prospectives for the advancement of NASICON-based ASSSMBs are outlined.

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)).

Development of solid-state electrolytes for sodium-ion battery–A short review

All-solid-state sodium-ion battery is regarded as the next generation battery to replace the current commercial lithium-ion battery, with the advantages of abundant sodium resources, low price and high-level safety. As one critical component in sodium-ion battery, solid-state electrolyte should possess superior operational safety and design simplicity, yet reasonable high room-temperature ionic conductivity. This paper gives a comprehensive review on the recent progress in solid-state electrolyte materials for sodium-ion battery, including inorganic ceramic/glass-ceramic, organic polymer and ceramic-polymer composite electrolytes, and also provides a comparison of the ionic conductivity in various solid-state electrolyte materials. The development of solid-state electrolytes suggests a bright future direction: all solid-state sodium-ion battery could be fully used to power all electric road vehicles, portable electronic devices and large-scale grid support.

Insight to defects regulation on sugarcane waste-derived hard carbon anode for sodium-ion batteries

A great deal of attention has been paid on developing plant-derived hard carbon(HC)materials as anodes for sodium-ion batteries(SIBs).So far,the regulation of HC has been handicapped by the well-known ambiguity of Na^(+)storage mechanism,which fails to differentiate the Na^(+)adsorption and Na^(+)insertion,and their relationship with the size of d-interlayer spacing and structural porosity.Herein,bagassederived HC materials have been synthesized through a combination of pyrolysis treatment and microwave activation.The combined protocol has enabled to synergistically control the d-interlayer spacing and porosity.Specifically,the microwave activation has created slit pores into HC and these pores allow for an enhanced Na^(+)adsorption with an increased sloping capacity,establishing a strong correlation between the porosity and sloping capacity.Meanwhile,the pyrolysis treatment promotes the graphitization and it contributes to an intensified Na^(+)insertion with an increased plateau capacity,proving that the plateau capacity is largely contributed by the Na^(+)insertion between interlayers.Therefore,the structural regulation of bagasse-derived HC has provided a proof on positively explaining the Na^(+)storage with HC materials.The structural changes in the pore size distribution,specific surface area,d-interlayer spacing,and the electrochemical properties have been comprehensively characterized,all supporting our understanding of Na^(+)storage mechanism.As a result,the HC sample with an optimized d-interlayer spacing and porosity has delivered an improved reversible capacity of 323.6 m Ah g^(-1) at 50 m A g^(-1).This work provides an understanding of Na^(+)storage mechanism and insights on enhancing the sloping/plateau capacity by rationally regulating the graphitization and porosity of HC materials for advanced SIBs.

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.

Investigation of sodium vanadate as a high-performance aqueous zinc-ion battery cathode

Due to the intrinsic advantages of nontoxicity, low-cost, and abundant resource of metallic zinc, aqueous zinc-ion batteries (ZIBs) have attracted universal interest [1,2]. Tremendous cathode materials have been exploited in aqueous ZIBs, such as manganese-based materials [3-11], Co-based materials [12,13] and vanadium-based materials [14-21].

Bi_2Se_3/C Nanocomposite as a New Sodium-Ion Battery Anode Material

Bi_2Se_3 was studied as a novel sodium-ion battery anode material because of its high theoretical capacity and high intrinsic conductivity. Integrated with carbon,Bi_2Se_3/C composite shows excellent cyclic performance and rate capability. For instance, the Bi_2Se_3/C anode delivers an initial capacity of 527 mAh g^(-10) at 0.1 A g^(-1) and maintains 89% of this capacity over 100 cycles. The phase change and sodium storage mechanism are also carefully investigated.