Constructing long-cycling crystalline C_(3)N_(4)-based carbonaceous anodes for sodium-ion battery via N configuration control

Carbon nitrides with two-dimensional layered structures and high theoretical capacities are attractive as anode materials for sodium-ion batteries while their low crystallinity and insufficient structural stability strongly restrict their practical applications.Coupling carbon nitrides with conductive carbon may relieve these issues.However,little is known about the influence of nitrogen(N)configurations on the interactions between carbon and C_(3)N_(4),which is fundamentally critical for guiding the precise design of advanced C_(3)N_(4)-related electrodes.Herein,highly crystalline C_(3)N_(4)(poly(triazine imide),PTI)based all-carbon composites were developed by molten salt strategy.More importantly,the vital role of pyrrolic-N for enhancing charge transfer and boosting Na+storage of C_(3)N_(4)-based composites,which was confirmed by both theoretical and experimental evidence,was spot-highlighted for the first time.By elaborately controlling the salt composition,the composite with high pyrrolic-N and minimized graphitic-N content was obtained.Profiting from the formation of highly crystalline PTI and electrochemically favorable pyrrolic-N configurations,the composite delivered an unusual reverse growth and record-level cycling stability even after 5000 cycles along with high reversible capacity and outstanding full-cell capacity retention.This work broadens the energy storage applications of C_(3)N_(4) and provides new prospects for the design of advanced all-carbon electrodes.

Rational manipulation of electrolyte to induce homogeneous SEI on hard carbon anode for sodium-ion battery

Sodium-ion batteries (SIBs) have great potential to be the next major energy storage devices due to their obvious advantages and developing advanced electrodes and electrolytes is urgently necessary to promote its future industrialization.However,hard carbon as a state-of-the-art anode of SIBs still suffers from the low initial Coulomb efficiency and unsatisfactory rate capability,which could be improved by forming desirable solid electrolyte interphases (SEI) to some extent.Indeed,the chemistry and morphology of these interfacial layers are fundamental parameters affecting the overall battery operation,and optimizing the electrolyte to dictate the quality of SEI on hard carbon is a key strategy.Hence,this review summarizes the recent research on SEI design by electrolyte manipulation from solvents,salts,and additives.It also presents some potential mechanisms of SEI formation in various electrolyte systems.Besides,the current advanced characterization techniques for electrolyte and SEI structure analyses have been comprehensively discussed.Lastly,current challenges and future perspectives of SEI formation on hard carbon anode for SIBs are provided from the viewpoints of its compositions,evolution processes,structures,and characterization techniques,which will promote SEI efficient manipulation and improve the performance of hard carbon,and further contribute to the development of SIBs.

Regulating solid electrolyte interphase film on fluorinedoped hard carbon anode for sodium-ion battery

For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However,the previous work focuses mainly on the intrinsic physicochemical property changes of the material,but little attention has been paid to the resulting interfacial regulation of the electrode surface,namely the formation of solid electrolyte interphase(SEI)film.In this work,element F,which has the highest electronegativity,was chosen as the doping source to,more effectively,tune the electronic structure of the hard carbon.The effect of F-doping on the physicochemical properties of hard carbon was not only systematically analyzed but also investigated with spectroscopy,optics,and in situ characterization techniques to further verify that appropriate F-doping plays a positive role in constructing a homogenous and inorganic-rich SEI film.The experimentally demonstrated link between the electronic structure of the electrode and the SEI film properties can reframe the doping optimization strategy as well as provide a new idea for the design of electrode materials with low reduction kinetics to the electrolyte.As a result,the optimized sample with the appropriate F-doping content exhibits the best electrochemical performance with high capacity(434.53 mA h g^(-1)at 20mA g^(-1))and excellent rate capability(141 mAh g^(-1)at 400 mA g^(-1)).

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.

Synergy mechanism of defect engineering in MoS_(2)/FeS_(2)/C heterostructure for high-performance sodium-ion battery

MoS_(2) is a promising anode material in sodium-ion battery technologies for possessing high theoretical capacity.However,the sluggish Na^(+) diffusion kinetics and low electronic conductivity hinder the promises.Herein,a unique MoS_(2)/FeS_(2)/C heterojunction with abundant defects and hollow structure(MFCHHS)was constructed.The synergy of defect engineering in MoS_(2),FeS_(2),and the carbon layer of MFCHHS with a larger specific surface area provides multiple storage sites of Na^(+)corresponding to the surface-controlled process.The MoS_(2)/FeS_(2)/C heterostructure and rich defects in MoS_(2) and carbon layer lower the Na^(+) diffusion energy barrier.Additionally,the construction of MoS_(2)/FeS_(2) heterojunction promotes electron transfer at the interface,accompanying with excellent conductivity of the carbon layer to facilitate reversible electrochemical reactions.The abundant defects and mismatches at the interface of MoS_(2)/FeS_(2) and MoS_(2)/C heterojunctions could relieve lattice stress and volume change sequentially.As a result,the MFCHHS anode exhibits the high capacity of 613.1 mA h g^(-1)at 0.5 A g^(-1) and 306.1 mA h g^(-1) at 20 A g^(-1).The capacity retention of 85.0%after 1400 cycles at 5.0 A g^(-1) is achieved.The density functional theory(DFT)calculation and in situ transmission electron microscope(TEM),Raman,ex-situ X-ray photon spectroscopy(XPS)studies confirm the low volume change during intercalation/deintercalation process and the efficient Na^(+)storage in the layered structure of MoS_(2) and carbon layer,as well as the defects and heterostructures in MFCHHS.We believe this work could provide an inspiration for constructing heterojunction with abundant defects to foster fast electron and Na^(+) diffusion kinetics,resulting in excellent rate capability and cycling stability.

Hollow sphere of heterojunction(NiCu)S/NC as advanced anode for sodium-ion battery

Metal sulfide is considered as a potential anode for sodium-ion batteries(SIBs),due to the high theoretical capacity,strong thermodynamic stability and low-cost.However,their cycle capacity and rate performance are limited by the excessive expansion rate and low intrinsic conductivity.Herein,heterogeneous hollow sphere NiS-Cu_(9)S_(5)/NC(labeled as(NiCu)S/NC)based on Oswald ripening mechanism was prepared through a simple and feasible methodology.From a structural perspective,the hollow structure provides an expansion buffer and raises the electrochemical active area.In terms of electron/ion during the cycles,Na^(+)storage mechanism is optimized by NiS/Cu_(9)S_(5)heterogeneous interface,which increases the storage sites and shortens the migration path of Na^(+).The formation of built-in electric field strengthens the electron/ion mobility.Based on the first principle calculations,it is further proved the formation of heterogeneous interfaces and the direction of electron flow.As the anode for SIBs,the synthesized(NiCu)S/NC delivers high reverse capacity(559.2 mA h g^(-1)at 0.5 A g^(-1)),outstanding rate performance(185.3 mA h g^(-1)at 15 A g^(-1)),long-durable stability(342.6 mA h g^(-1)at 4 A g^(-1)after 1500cycles,150.0 m A h g^(-1)at 10 A g^(-1)after 20,000 cycles with 0.0025%average attenuation rate).The matching cathode electrode Na_(3)V_(2)(PO_(4))_(3)/C is assembled with(NiCu)S/NC for the full-battery that achieves high energy density(253.7 W h kg^(-1))and reverse capacity(288.7 mA h g^(-1)).The present work provides a distinctive strategy for constructing electrodes with excellent capacity and stability for SIBs.

Spinel lithium titanate (Li_4Ti_5O_(12)) as novel anode material for room-temperature sodium-ion battery

This is the first time that a novel anode material, spinel Li4Ti5O12 which is well known as a ＂zero-strain＂ anode material for lithium storage, has been introduced for sodium-ion battery. The Li4Ti5O12 shows an average Na storage voltage of about 1.0 V and a reversible capacity of about 145 mAh/g, thereby making it a promising anode for sodiumion battery. Ex-situ X-ray diffraction （XRD） is used to investigate the structure change in the Na insertion/deinsertion process. Based on this, a possible Na storage mechanism is proposed.

A green route to synthesize low-cost and high-performance hard carbon as promising sodium-ion battery anodes from sorghum stalk waste

Sodium-ion batteries(SIBs) have been considered to be potential candidates for next-generation low-cost energy storage systems due to the low-cost and abundance of Na resources. However, it is a big challenge to find suitable anode materials with low-cost and good performance for the application of SIBs. Hard carbon could be a promising anode material due to high capacity and expectable low-cost if originating from biomass. Herein, we report a hard carbon material derived from abundant and abandoned biomass of sorghum stalk through a simple carbonization method. The effects of carbonization temperature on microstructure and electrochemical performance are investigated. The hard carbon carbonized at 1300 ℃ delivers the best rate capability(172 mAh g^(-1) at 200 mA g^(-1)) and good cycling performance(245 mAh g^(-1) after 50 cycles at 20 mA g^(-1),96% capacity retention). This contribution provides a green route for transforming sorghum stalk waste into "treasure"of promising low-cost anode material for SIBs.

Hollow Bio-derived Polymer Nanospheres with Ordered Mesopores for Sodium-Ion Battery

Bio-inspired hierarchical self-assembly provides elegant and powerful bottom-up strategies for the creation of complex materials.However,the current self-assembly approaches for natural bio-compounds often result in materials with limited diversity and complexity in architecture as well as microstructure.Here,we develop a novel coordination polymerization-driven hierarchical assembly of micelle strategy,using phytic acid-based natural compounds as an example,for the spatially controlled fabrication of metal coordination bio-derived polymers.The resultant ferric phytate polymer nanospheres feature hollow architecture,ordered meso-channels of^12 nm,high surface area of 401 m2 g−1,and large pore volume of 0.53 cm3 g−1.As an advanced anode material,this bio-derivative polymer delivers a remarkable reversible capacity of 540 mAh g−1 at 50 mA g−1,good rate capability,and cycling stability for sodium-ion batteries.This study holds great potential of the design of new complex bio-materials with supramolecular chemistry.

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.

Ultrahigh rate binder-free Na_3V_2(PO_4)_3/carbon cathode for sodium-ion battery

Sodium ion batteries （SIBs） are very promising for large-scale energy storage in virtue of its high energy density, abundant sodium resources and low environmental impact, etc. However, it is still a big chal- lenge to develop high-performance and durable cathode materials for SIBs. Among different candidate materials, Na_3V_2（PO_4）_3 has attracted great attentions due to its high theoretical capacity （117 mAh/g）, stable framework structure and excellent ionic conductivity. However, Na_3V_2（PO_4）_3 delivers inferior rate capability and cycling stability due to its poor electronic conductivity. In this work, free-standing Na_3V_2（PO_4）_3/carbon nanofiber membranes are synthesized by an electrospinning-sintering mute. The sample could deliver excellent cycling capability with specific capacity of 112 mAh/g at 1 C after 250 cycles and ultrahigh rate capability with 76.9 mAh/g even at 100 C, which is superior to many state-of- the-art SIB cathode materials. This can be attributed to the hierarchically distributed Na_3V_2（PO_4）_3 crystals in carbon nanofiber network, which possesses outstanding electronicfionic conductivity and thus leads to an ultrahigh rate capabilitY.

Effects of Cr doping on structural and electrochemical properties of Li_(4)Ti_(5)O_(12) nanostructure for sodium-ion battery anode

Sodium-ion batteries are considered as promising alternatives to lithium-ion batteries,owing to their low cost and abundant raw materials.Among the several candidate materials for the anode,spinel-type Li_(4)Ti_(5)O_(12)has potential owing to its superior safety originating from an appropriate operating voltage and the reversible Na^(+)intercalation properties.However,a low diffusion coefficient for Na^(+)and the insulating nature of LTO remains challenging for practical sodium-ion battery systems.Herein,we present a strategy for integrating physical and chemical approaches to achieve superior electrochemical properties in LTO.We demonstrate that carefully controlling the amount of Cr doping is crucial to enhance the electrochemical properties of nanostructured LTO.Optimized Cr doped LTO shows a superior reversible capacity of 110 m Ah g^(-1) after 400 cycles at 1 C,with a three-fold higher capacity(75 m Ah g^(-1))at 10 C compared with undoped LTO material.This suggests that appropriately Cr doped nanostructured LTO is a promising anode material for sodium-ion batteries.

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.

Interwoven scaffolded porous titanium oxide nanocubes/carbon nanotubes framework for high-performance sodium-ion battery

Supercapacitor-like Na-ion batteries have attracted much attention due to the high energy density of batteries and power density of capacitors.Titanium dioxide(TiO_(2)),is a promising anode material.Its performance is however seriously hindered by its low electrical conductivity and the sluggish diffusion of sodium ions(Na^(+))in the TiO_(2)matrix.Herein,this work combines porous TiO_(2)nanocubes with carbon nanotubes(CNTs)to enhance the electrical conductivity and accelerate Na^(+)diffusivity for Na-ion batteries(NIBs).In this composite,an interwoven scaffolded TiO_(2)/CNTs framework is formed to provide abundant channels and shorter diffusion pathways for electrons and ions.The in-situ X-ray diffraction and cyclic voltammetry confirm the low strain and superior transport kinetics in Na^(+)intercalation/extraction processes.In addition,the chemically bonded TiO_(2)/CNTs hybrid provides a more feasible channel for Na^(+)insertion/extraction with a much lower energy barrier.Consequently,the TiO_(2)/CNTs composite exhibits excellent electrochemical performance with a capacity of 223.4 m Ah g^(-1)at 1 C and a capacity of 142.8 m Ah g^(-1)at 10 C(3.35 A g^(-1)).The work here reveals that the combination of active materials with CNTs can largely improve the utilization efficiency and enhance their sodium storage.

A new Tin-based O3-Na_(0.9)[Ni_(0.45-x/2)Mn_xSn_(0.55-x/2)]O_2 as sodium-ion battery cathode

Recently,sodium-ion batteries(SIBs),regarded as promising supplements for lithium-ion batteries(LIBs),especially in the large-scale energy storage field,are attracting more and more attention.However,the limited suitable cathode materials hinder the wide commercialization of SIBs.Given this aspect,in this work,a new layered oxide with 4d metal Tin was synthesized and investigated as cathode material for SIBs.Two optimized sodium-deficient O3-Na_(0.9)Ni_(0.45)Sn_(0.55)O_2and O3-Na_(0.9)Ni_(0.4)Mn_(0.1)Sn_(0.5)O_2were selected for comprehensive investigation,both of which exhibited high operating voltage of around 3.45 V with smooth charge/discharge curves.In comparison,O3-Na_(0.9)Ni_(0.4)Mn_(0.1)Sn_(0.5)O_2shows a higher reversible capacity(65 m A h/g,0.1 C),better rate capability and cycling stability than that of O3-Na_(0.9)Ni_(0.45)Sn_(0.55)O_2(50 mA h/g,0.1 C),indicating that a small amount of Mn-substitution can improve the electrochemical performance.This work presents a new possibility of discovering potential cathode candidates by exploring the Tin-based layered oxides.

Tailoring interphase structure to enable high-rate, durable sodium-ion battery cathode

Na-based layered transition metal oxides with O_(3)-type structure have been considered to be promising cathodes for Na-ion batteries. However, the intrinsically limited Na-ion conductivity induced by the Otype Na-coordinate environment compromises their rate and cycle capability, hindering their practical application. Here, we report an interphase-structure tailoring strategy that improves the electrochemical properties of O_(3)-type layered cathodes achieved through surface coating and doping processes.Specifically, a Zr-doped interphase structure is designed in the model compound NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2) using the ionic conductor Na_(3)Zr_(2)Si_(2)PO_(12) as the surface coating material and Zr-dopant provider. We discover that the modified NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)cathode shows a stable Na-storage structure as well as an enhanced rate/cycle capability. Combined with theoretical calculations, it is suggested that the superior electrochemical performances originate from the Zr-doped interphase structure, which has an enlarged Na layer spacing that forms favorable Na-ion diffusion channels. This work highlights a general material interface optimization method which opens a new perspective for fabricating high-performance electrodes for Na-ion batteries and beyond.

Interfacial engineering of the layered oxide cathode materials for sodium-ion battery

The layered metal oxides are reviewed as the hopeful cathode materials for high-performance sodium-ion batteries(SIBs)due to their large theoretical capacity,favorable two-dimensional(2D)ion diffusion channel,and simple manipuility.However,their cycling stability,rate capability,and thermal stability are still significantly concerned and highlighted before further practical application.The chemical,mechanical and electrochemical stability of the cathode–electrolyte interfaces upon cycling is of great significance.Herein,the unique structural and electrochemical properties of the layered oxide cathode materials for SIB are reviewed.The mechanism of bulk/surface degradation induced by oxygen evolution,phase transition,microcrack,and electrolyte decomposition is thoroughly understood.Furthermore,the interfacial engineering to construct stable interface through various effective methods is fully discussed.The future outlook and challenges for interfacial engineering in this filed are also summarized.This review should shed light on the rational design and construct of robust interface for applications of superior layered oxide cathodes in SIB and may suggest future research directions.

Fluorophosphates and fluorosulfates cathode materials: Progress towards high energy density sodium-ion battery

The rapid diffusion of renewable energy boosts the wide deployment of large-scale energy storage system.With the low cost and high crustal abundance,sodium-ion battery(SIB)technology is expected to become a dominant technology in that area in the future.Toward the practical application,novel cathode materials are urged to develop that show high energy density without sacrificing their cost and benignity to the environment.While the years of many studies,this still remains a huge challenge to battery scientists.In this review,we discuss recent breakthroughs in SIB cathode materials with high energy density,namely fluorphosphates and fluorosulfates.The design of materials,the crystal structure,the electrochemical performance,and the underlaying intercalation mechanism are systematically reviewed.Useful strategies and research directions are also provided to advance future high-energy,low-cost,and ecofriendly cathode materials for next generation SIB.

Reinforced concrete-like Na_(3.5)V_(1.5)Mn_(0.5)(PO_(4))_(3)@graphene hybrids with hierarchical porosity as durable and high-rate sodium-ion battery cathode

Realizing high-rate capability and high-efficiency utilization of polyanionic cathode materials is of great importance for practical sodium-ion batteries(SIBs) since they usually suffer from extremely low electronic conductivity and limited ionic diffusion kinetics. Herein, taking Na_(3.5)V_(1.5)Mn_(0.5)(PO_(4))_(3)(NVMP) as an example, a reinforced concrete-like hierarchical and porous hybrid(NVMP@C@3DPG) built from 3D graphene(“rebar”) frameworks and in situ generated carbon coated NVMP(“concrete”) has been developed by a facile polymer assisted self-assembly and subsequent solid-state method. Such hybrids deliver superior rate capability(73.9 m Ah/g up to 20 C) and excellent cycling stability in a wide temperature range with a high specific capacity of 88.4 m Ah/g after 5000 cycles at 15 C at room temperature, and a high capacity retention of 97.1% after 500 cycles at 1 C(-20 ℃), and maintaining a high reversible capacity of 110.3 m Ah/g in full cell. This work offers a facile and efficient strategy to develop advanced polyanionic cathodes with high-efficiency utilization and 3D electron/ion transport systems.