Surface encapsulation of layered oxide cathode material with NiTiO_(3) for enhanced cycling stability of Na-ion batteries

In Na-ion batteries,O3-type layered oxide cathode materials encounter challenges such as particle cracking,oxygen loss,electrolyte side reactions,and multi-phase transitions during the charge/discharge process.This study focuses on surface coating with NiTiO_(3) achieved via secondary heat treatment using a coating precursor and the surface material.Through in-situ x-ray diffraction(XRD)and differential electrochemical mass spectrometry(DEMS),along with crystal structure characterizations of post-cycling materials,it was determined that the NiTiO_(3) coating layer facilitates the formation of a stable lattice structure,effectively inhibiting lattice oxygen loss and reducing side reaction with the electrolyte.This enhancement in cycling stability was evidenced by a capacity retention of approximately 74%over 300 cycles at 1 C,marking a significant 30%improvement over the initial sample.Furthermore,notable advancements in rate performance were observed.Experimental results indicate that a stable and robust surface structure substantially enhances the overall stability of the bulk phase,presenting a novel approach for designing layered oxide cathodes with higher energy density.

Growth of SnO_2 Nanoflowers on N-doped Carbon Nanofibers as Anode for Li-and Na-ion Batteries

It is urgent to solve the problems of the dramatic volume expansion and pulverization of SnO_2 anodes during cycling process in battery systems. To address this issue, we design a hybrid structure of N-doped carbon fibers@SnO_2 nanoflowers(NC@SnO_2) to overcome it in this work. The hybrid NC@SnO_2 is synthesized through the hydrothermal growth of SnO_2 nanoflowers on the surface of N-doped carbon fibers obtained by electrospinning. The NC is introduced not only to provide a support framework in guiding the growth of the SnO_2 nanoflowers and prevent the flower-like structures from agglomeration, but also serve as a conductive network to accelerate electronic transmission along one-dimensional structure effectively. When the hybrid NC@SnO_2 was served as anode, it exhibits a high discharge capacity of 750 Ah g^(-1) at 1 A g^(-1) after 100 cycles in Li-ion battery and 270 mAh g^(-1) at 100 mA g^(-1) for 100 cycles in Na-ion battery, respectively.

Hard carbon derived from rice husk as low cost negative electrodes in Na-ion batteries

Here,we report the synthesis of hard carbon materials(RH) made from natural rice husk through a single pyrolysis process and their application as an anode in sodium-ion batteries.The studies show that the electrochemical properties of RHs are affected by the treatment temperatures,which determine the materials morphology,in particular,their degree of graphitization and extent of continuous channels(nanovoids).The latter are accessible to sodium ions and significantly contribute to charge storage capacity of the produced anodes.The RHs obtained at 1600 °C deliver the highest reversible capacity of276 mAh g^(-1) mainly due to insertion of sodium ions into the nanovoids.This work deepens the basic understanding of the influence of the carbonization temperature on the sodium storage mechanism.

Hard carbon derived from coconut shells,walnut shells,and corn silk biomass waste exhibiting high capacity for Na-ion batteries

In recent years,hard carbon materials have gained significant interest as anode materials for Na-ion batteries.Biomass waste is considered one of the most interesting,renewable,available,and cost-effective precursor to obtain hard carbon(HC);however,HC properties must be finely tuned to achieve performance comparable to those provided by Li-ion batteries.In this work,three biomass wastes(coconut shells,walnut shells,and corn silk) were evaluated as potential precursors for HC preparation involving a pyrolysis process and subsequent acid washing to remove the inorganic impurities.All obtained materials exhibited low and similar specific surface areas(<10 m^(2)·g^(-1)), but they presented different structures and surface functionalities.The walnut shell HC possessed a lower amount of inorganic impurities and oxygen-based functional groups compared to the coconut shell and corn silk HCs,leading to higher initial coulombic efficiency(iCE).The structural organization was higher in the case of the walnut shell HC,while the corn silk HC revealed a heterogeneous structure combining both highly disordered carbon and localized graphitized domains.All HCs delivered high initial reversible capacities between 293 and 315 mAh g^(-1) at 50 mA g^(-1) current rate,which remained rather stable during long-term cycling.The best capacity(293 mAh g^(-1) after 100 charge/discharge cycles) and highest capacity retention(93%) was achieved in walnut HCs in half-cells,which could be associated with its higher sp2 C content,better organized structure,and fewer impurities.An "adsorption-insertion" Na storage mechanism is suggested based on several techniques.The walnut HCs exhibited an attractive energy density of 279 Wh/kg when tested in full cells.

Recent advances on flexible electrodes for Na-ion batteries and Li–S batteries

Flexible energy storage devices are essential for emerging flexible electronics. The existing state-of-the-art Li-ion batteries are slowly reaching their limitation in terms of cost and energy density. Hence, flexible Na-ion batteries (SIBs) with abundanee Na resources and Li-S batteries with high energy density become the alternative for the Li-ion batteries in future. This review summarizes the recent advances in the development of flexible electrode materials for SIBs with metallic matrix and carb on aceous matrix such as carb on nano-tubes, carbon nano-fiber, graphene, carbon cloth, carbon fiber cloth, and cotton textiles. Then, the potential prototype flexible full SIBs are discussed. Further, the recent progress in the development of flexible electrode materials for Li-S batteries based on carb on nano-fiber, carb on nano-tubes, graphene, and cotton textiles is reviewed. Moreover, the design strategies of suitable interlayer, separator, electrolyte, and electrodes to prevent the dissolution and shuttle effect of polysulfides in flexible Li-S batteries are provided. Finally some prospective investigation trends towards future research of flexible SIBs and Li-S batteries are also proposed and discussed. The scientific and engineering knowledge gained on flexible SIBs and Li-S batteries provides conceivable development for practical application in near future.

Failure analysis with a focus on thermal aspect towards developing safer Na-ion batteries

Safety requirements stimulate Na-based batteries to evolve from high-temperature Na–S batteries to room-temperature Na-ion batteries(NIBs).Even so,NIBs may still cause thermal runaway due to the external unexpected accidents and internal high activity of electrodes or electrolytes,which has not been comprehensively summarized yet.In this review,we summarize the significant advances about the failure mechanisms and related strategies to build safer NIBs from the selection of electrodes,electrolytes and the construction of electrode/electrolyte interfaces.Considering the safety risk,the thermal behaviors are emphasized which will deepen the understanding of thermal stability of different NIBs and accelerate the exploitation of safe NIBs.

Metal–organic framework derived hierarchical porous TiO_2 nanopills as a super stable anode for Na-ion batteries

Hierarchical porous TiOnanopills were synthesized using a titanium metal-organic framework MIL-125（Ti） as precursor. The as-synthesized TiOnanopills owned a large specific surface area of 102 m/g and unique porous structure. Furthermore, the obtained TiOnanopills were applied as anode materials for Na-ion batteries for the first time. The as-synthesized TiOnanopills achieved a high discharge capacity of 196.4 m Ah/g at a current density of 0.1 A/g. A discharge capacity of 115.9 m Ah/g was obtained at a high current density of 0.5 A/g and the capacity retention was remained as high as 90% even after 3000 cycles. The excellent electrochemical performance can be attributed to its unique hierarchical porous feature.

Recent Progress in Presodiation Technique for High-Performance Na-Ion Batteries

Na-ion batteries(NIBs) have been attracting growing interests in recent years with the increasing demand of energy storage owing to their dependence on more abundant Na than Li. The exploration of the industrialization of NIBs is also on the march, where some challenges are still limiting its step. For instance, the relatively low initial Coulombic efficiency(ICE) of anode can cause undesired energy density loss in the full cell. In addition to the strategies from the sight of materials design that to improve the capacity and ICE of electrodes, presodiation technique is another important method to efficiently offset the irreversible capacity and enhance the energy density. Meanwhile, the slow release of the extra Na during the cycling is able to improve the cycling stability.In this review, we would like to provide a general insight of presodiation technique for high-performance NIBs.The recent research progress including the principles and strategies of presodiation will be introduced, and some remaining challenges as well as our perspectives will be discussed. This review aims to exhibit the basic knowledge of presodiation to inspire the researchers for future studies.

Hard carbons derived from pine nut shells as anode materials for Na-ion batteries

Hard carbons as promising anode materials for Na-ion batteries(NIBs) have captured extensive attention because of their low operation voltage, easy synthesis process, and competitive specific capacity. However, there are still several disadvantages, such as high cost and low initial coulombic efficiency, which limit their large-scale commercial applications.Herein, pine nut shells(PNSs), a low-cost biomass waste, are used as precursors to prepare hard carbon materials. Via a series of washing and heat treatment procedures, a pine nut shell hard carbon(PNSHC)-1400 sample has been obtained and delivers a reversible capacity of around 300 mAh/g, a high initial coulombic efficiency of 84%, and good cycling performance. These excellent Na storage properties indicate that PNSHC is one of the most promising candidates of hard carbon anodes for NIBs.

Mg-doped layered oxide cathode for Na-ion batteries

Na-ion batteries(NIBs)are regarding as the optimum complement for Li-ion batteries along with the rapid development of stationary energy storage systems.In order to meet the commercial demands of cathodes for NIBs,O3-type Cu containing layered oxide Na_(0.9)0Cu_(0.22)Fe_(0.30)Mn_(0.48O_(2))with good comprehensive performance and low-cost element components is very promising for the practical use.However,only part of the Cu^(3+)/Cu^(2+)redox couple participated in the redox reaction,thus impairing the specific capacity of the cathode materials.Herein,Mg2+-doped O3-Na0.90Mg0.08Cu0.22Fe0.30Mn0.40O_(2)layered oxide without Mn3+was synthesized successfully,which exhibited improved reversible specific capacity of 118 mAh/g in the voltage range of 2.4-4.0 V at 0.2 C,corresponding to the intercalation/deintercalation of 0.47 Na+(0.1 more than that of Na_(0.9)0Cu_(0.22)Fe_(0.30)Mn_(0.48O_(2))).This work demonstrates an important strategy to obtain advanced layered oxide cathodes for NIBs.

Anionic redox reaction mechanism in Na-ion batteries

Na-ion batteries(NIBs),as one of the next-generation rechargeable battery systems,hold great potential in large-scale energy storage applications owing to the abundance and costeffectiveness of sodium resources.Despite the extensive exploration of electrode materials,the relatively low attainable capacity of NIBs hinders their practical application.In recent years,the anionic redox reaction(ARR)in NIBs has been emerging as a new paradigm to deliver extra capacity and thus offers an opportunity to break through the intrinsic energy density limit.In this review,the fundamental investigation of the ARR mechanism and the latest exploration of cathode materials are summarized,in order to highlight the significance of reversible anionic redox and suggest prospective developing directions.

Enhancing the cycling stability of Na-ion batteries by bonding MoS2 on assembled carbon-based materials

Room temperature Na-ion batteries(SIBs) show great potential for use as renewable energy storage systems.However, the large-scale application of SIBs has been hindered by the lack of an ideal SIBs anode material. We synthesized MoS2 on carbonized graphene-chitosan(G-C) using the hydrothermal method. The strong interaction between the MoS2 and the G-C greatly improved the electron transport rate and maintained the structural stability of the electrode, which lead to both an excellent rate capability and long cycle stability. The G-C monolith was proven to enhance the electrical conductivity of the composites and served as a matrix for uniformly dispersing active MoS2 nanosheets(NSs), as well as being a buffer material to adapt to changes in volume during the cycle.Serving as an anode material for SIBs, the MoS2-G-C electrode showed good cycling stability(527.3mAh g-1 at100 m A g-1 after 200 cycles), excellent rate capability, and a long cycle life(439.1 m Ah g-1 at 1 A g-1 after 200 cycles).

Two-step carbon modification of NaTi_2(PO_4)_3 with improved sodium storage performance for Na-ion batteries

NASICON-type structured NaTi2(PO4)3 has been regarded as a promising anode material for non-aqueous and aqueous Na-ion batteries,whereas its sodium storage performance was greatly restricted by its inherent inferior electronic conductivity.In the present work,a two-step carbon modification method using prefabricated carbon spheres as support and phenolic resin as carbon source was proposed to prepare advanced NaTi2(PO4)3/C.The as-prepared composite with carbon spheres displayed a much higher reversible capacity(126.7 mA?h/g vs 106.7 mA?h/g at 0.5C)than the control sample without carbon spheres.Superior rate capability with discharge capacities of 115.1,95.5,80.8 mAh/g at 1C,10C,20C,respectively and long-term cycling stability with capacity retention of 92.4%after 1000 cycles at 5C were also observed.Owing to the designing of two-step carbon modification,although the as-prepared sample shows much smaller surface area,it possesses much better conductive network and more uniform particle distribution,resulting in higher electronic conductivity and faster ionic conductivity,thereby superior sodium storage ability at high rate.

P2-Na_(2/3)Ni_(2/3)Te_(1/3)O_(2)Cathode for Na-ion Batteries with High Voltage and Excellent Stability

Air-stable layered structured cathodes with high voltage and good cycling stability are highly desired for the practical application of Na-ion batteries.Herein,we report a P2-Na_(2/3)Ni_(2/3)Te_(1/3)O_(2) cathode that is stable in ambient air with an average operating voltage of~3.8 V,demonstrating excellent cycling stability with a capacity retention of more than 92.7%after 500 cycles at 20 mA g^(-1) and good rate capability with 91.9%capacity utilization at 500 mA g^(-1) with respect to capacity at 5 mA g^(-1) between 2.0 and 4.0 V.When the upper cutoff voltage is increased to 4.4 V,P2-Na_(2/3)Ni_(2/3)Te_(1/3)O_(2) delivers a reversible capacity of 71.9 mAh g^(-1) and retains 91.8%of the capacity after 100 cycles at 20 mA g^(-1).The charge compensation during charge/discharge is mainly due to the redox couple of Ni^(2+)/Ni^(3+)in the host with a small amount of contribution from oxygen.The stable structure of the material without phase transformation and with small volume change during charge-discharge allows it to give excellent cycle performance especially when the upper cutoff voltage is not higher than 4.2 V.

Designing a P2-type cathode material with Li in both Na and transition metal layers for Na-ion batteries

P2-type layered oxides have been considered as promising cathode materials for Na-ion batteries,but the capac-ity decay resulting from the Na+/vacancy ordering and phase transformation limits their future large-scale applica-tions.Herein,the impact of Li-doping in different layers on the structure and electrochemical performance of P2-type Na_(0.7)Ni_(0.35)Mn_(0.65)O_(2) is investigated.It can be found that Li ions successfully enter both the Na and transition metal layers.The strategy of Li-doping can improve the cycling stability and rate capability of P2-type layered oxides,which promotes the development of high-performance Na-ion batteries.

Hollow carbon microbox from acetylacetone as anode material for sodium-ion batteries

Carbon-based materials have attracted much interest as one of the promising anodes for sodium-ion batteries. However, low utilization of electrolyte and slow ion-transfer rate during electrochemical process hinder the further application of traditional bulk carbon. In order to enhance the diffusion kinetics and maintain the reversibility, hierarchical hollow carbon microbox was successfully prepared through a tunable bottom-up self-template routine for sodium-ion batteries. During annealing process, the morphology construction and activation happened synchronously. Based on that, a range of cross-linked porous nanosheet and hollow microbox were attained by manipulating reactant condition. The generation of texture and physical property are analyzed and are established linkages related to the electrochemical behavior. As results depicted in kinetic exploration and simulation based on cyclic voltammetry, the surfacecontrolled electrochemical behavior gradually turns to be the diffusion-controlled behavior as the hollow microbox evolves to porous nanosheet. The probable reason is that the rational microstructure/texture design leads to the accelerated diffusion kinetic procedure and the reduced concentration difference polarization. Sodium storage mechanism was deduced as reversible binding of Na-ions with local defects,including vacancies on sp2 graphitic layers, at the edges of flakes and other structural defects instead of intercalation. Bestowed by the morphology design, the broad pore width distribution, abundant defects/active sites and surface functionality, hollow microbox electrode delivers great electrochemical performances. This work is expected to propose a novel and effective strategy to prepare tunable hierarchical hollow carbon microbox and induce the fast kinetic of carbon anode material.

Biphase-to-monophase structure evolution of Na_(0.766+x)Li_(x)Ni_(0.33-x)Mn_(0.5)Fe_(0.1)Ti_(0.07)O_(2) toward ultradurable Na-ion batteries

Layered composite oxide materials with O3/P2 biphasic crystallographic structure typically demonstrate a combination of high capacities of the O3 phase and high operation voltages of the P2 phase.However,their practical applications are seriously obstructed by difficulties in thermodynamic phase regulation,complicated electrochemical phase transition,and unsatisfactory cycling life.Herein,we propose an efficient structural evolution strategy from biphase to monophase of Na_(0.766+x)Li_(x)Ni_(0.33-x)Mn_(0.5)Fe_(0.1)Ti_(0.07)O_(2) through Li+substitution.The role of Li+substitution not only simplifies the unfavorable phase transition by altering the local coordination of transition metal(TM)cations but also stabilizes the cathode–electrolyte interphase to prevent the degradation of TM cations during battery cycling.As a result,the thermodynamically robust O_(3)-Na_(0.826)Li_(0.06)Ni_(0.27)Mn_(0.5)Fe_(0.1)Ti_(0.07)O_(2) cathode delivers a high capacity of 139.4 mAh g^(-1) at 0.1 C and shows prolonged cycling life at high rates,with capacity retention of 81.6%at 5 C over 500 cycles.This work establishes a solid relationship between the thermodynamic structure evolution and electrochemistry of layered cathode materials,contributing to the development of long-life sodium-ion batteries.

Construction of metal-organic framework-derived Al-doped Na_(3)V_(2)(PO_(4))_(3)cathode materials for high-performance recharge-able Na-ion batteries

Na_(3)V_(2)(PO_(4))_(3)(NVP)has emerged as one of the most promising cathode materials for sodium-ion batteries(SIBs)owing to its high ionic conductivity and high theoretical energy density.However,the inherent inferior conductivity of NVP prevents its achievement of the theoretical energy density even at low rates,thereby limiting the practical application of NVP in massive energy storage.Here,Al^(3+)-doped Na_(3)V_(2−x)Al_(x)(PO_(4))_(3)(NVAP)materials derived from aluminum terephthalate(MIL-53(Al))were synthesized for the first time,and the effects of Al3+doping on the structural and electrochemical performances of NVP were investigated.The NVAP mate-rials,particularly Na_(3)V_(1.97)Al_(0.03)(PO_(4))_(3)(NVAP2),exhibited superior cycling performance and rate capabilities compared with the NVP material.NVAP2 exhibited a good rate capability,with high reversible discharge capacities of 111.6,110.3,108.9,106.6,103.4,96.9,and 88.7 mAh g^(−1)at 0.1,0.2,0.5,1,2,5,and 10C rates,respectively.Moreover,the NVAP2 material exhibited a prominent initial discharge capacity of 102.3 mAh g^(−1)and maintained an excellent capacity retention rate of 92.0%after 2000 cycles at 10C,indicating significant cycling stability.Overall,this work provides an efficient technique for enhancing the electrochemical proper-ties of cathode materials with a sodium superionic conductor structure for SIBs.

Compositionally graded high-voltage P2-type cathode with superior structural stability and redox kinetics for advanced Na-ion batteries

Layered P2-type cathodes with high voltage,large capacity,and easy synthesis show great potential for developing sodium(Na)-ion batteries(NIBs).However,the P2–O2 phase transition makes their structural degradation and the Na^(+)/vacancy ordering lowers their redox kinetics.Here,we rationally propose a compositionally graded P2-type cathode,where nickel(Ni)and manganese(Mn)fractions decrease gradually,and cobalt(Co)content increases contiguously from the inside to the outside of a secondary particle.Inside these particles,the Ni/Mn-based compound delivers high capacity and high voltage.On the surface of particles,the Co/Mn-based solid solution offers a stable buffer matrix.Benefiting from these synergistic effects,this graded P2-type cathode shows the elimination of P2–O2 transformation even when charged to 4.4 V,which enables good structural stability,maintaining capacity retention reaching~80%within 300 cycles.Moreover,the Na^(+)/vacancy ordering superstructure is further suppressed,and the Na^(+)diffusion kinetics is significantly improved.The proposed graded structure with optimized chemical composition offers a new perspective for eliminating the unwanted phase transition and thus enhancing the electrochemistry of high-voltage layered cathodes for advanced NIBs.

High-Performance Na-Ion Storage of S-Doped Porous Carbon Derived from Conjugated Microporous Polymers

Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials for NIBs.However,the current methods for S doping in carbons normally involve toxic precursors or rigorous conditions.In this work,we report a creative and facile strategy for preparing S-doped porous carbons(SCs)via the pyrolysis of conjugated microporous polymers(CMPs).Briefly,thiophene-based CMPs served as the precursors and doping sources simultaneously.Simple direct carbonization of CMPs produced S-doped carbon materials with highly porous structures.When used as an anode for NIBs,the SCs exhibited a high reversible capacity of 440 mAh g?1 at 50 mA g?1 after 100 cycles,superior rate capability,and excellent cycling stability(297 mAh g?1 after 1000 cycles at 500 mA g?1),outperforming most S-doped carbon materials reported thus far.The excellent performance of the SCs is attributed to the expanded lattice distance after S doping.Furthermore,we employed ex situ X-ray photoelectron spectroscopy to investigate the electrochemical reaction mechanism of the SCs during sodiation-desodiation,which can highlight the role of doped S for Na-ion storage.