Designing Conformal Electrode-electrolyte Interface by Semi-solid NaK Anode for Sodium Metal Batteries

Solid-state Na metal batteries(SSNBs),known for its low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of NaK alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the intimate contact of electrode-electrolyte interface.Additionally,the filling of SiO_(2)nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 h.The full cell coupled with Na_(3)V_(3)(PO_(4))_(2)cathodes had an initial discharge capacity of 106.8 mAh·g^(-1)with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1)even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.

Unraveling the incompatibility mechanism of ethylene carbonate-based electrolytes in sodium metal anodes

Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.EC is also the most widely used electrolyte solvent in sodium ion batteries.However,compared to lithium metal,sodium metal(Na)shows higher activity and reacts violently with EC-based electrolyte(NaPF_(6)as solute),which leads to the failure of sodium metal batteries(SMBs).Herein,we reveal the electrochemical instability mechanism of EC on sodium metal battery,and find that the com-bination of EC and NaPF_(6) is electrically reduced in sodium metal anode during charging,resulting in the reduction of the first coulombic efficiency,and the continuous consumption of electrolyte leads to the cell failure.To address the above issues,an additive modified linear carbonate-based electrolyte is provided as a substitute for EC based electrolytes.Specifically,ethyl methyl carbonate(EMC)and dimethyl carbon-ate(DMC)as solvents and fluoroethylene carbonate(FEC)as SEI-forming additive have been identified as the optimal solvent for NaFP_(6)based electrolyte and used in Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))/Na batteries.The batter-ies exhibit excellent capacity retention rate of about 80%over 1000 cycles at a cut-off voltage of 4.3 V.

Dendrite‐free lithium and sodium metal anodes with deep plating/stripping properties for lithium and sodium batteries

Although lithium(Li)and sodium(Na)metals can be selected as the promising anode materials for next‐generation rechargeable batteries of high energy density,their practical applications are greatly restricted by the uncontrollable dendrite growth.Herein,a platinum(Pt)–copper(Cu)alloycoated Cu foam(Pt–Cu foam)is prepared and then used as the substrate for Li and Na metal anodes.Owing to the ultrarough morphology with a threedimensional porous structure and the quite large surface area as well as lithiophilicity and sodiophilicity,both Li and Na dendrite growths are significantly suppressed on the substrate.Moreover,during Li plating,the lithiated Pt atoms can dissolve into Li phase,leaving a lot of microsized holes on the substrate.During Na plating,although the sodiated Pt atoms cannot dissolve into Na phase,the sodiation of Pt atoms elevates many microsized blocks above the current collector.Either the holes or the voids on the surface of Pt–Cu foam what can be extra place for deposited alkali metal,what effectively relaxes the internal stress caused by the volume exchange during Li and Na plating/stripping.Therefore,the symmetric batteries of Li@Pt–Cu foam and Na@Pt–Cu foam have both achieved long‐term cycling stability even at ultrahigh areal capacity at 20 mAh cm−2.

Manipulating metal-sulfur interactions for achieving high-performance S cathodes for room temperature Li/Na-sulfur batteries

Rechargeable lithium/sodium-sulfur batteries working at room temperature(RT-Li/S,RT-Na/S)appear to be a promising energy storage system in terms of high theoretical energy density,low cost,and abundant resources in nature.They are,thus,considered as highly attractive candidates for future application in energy storage devices.Nevertheless,the solubility of sulfur species,sluggish kinetics of lithium/sodium sulfide compounds,and high reactivity of metallic anodes render these cells unstable.As a consequence,metal-sulfur batteries present low reversible capacity and quick capacity loss,which hinder their practical application.Investigations to address these issues regarding S cathodes are critical to the increase of their performance and our fundamental understanding of RT-Li/S and RT-Na/S battery systems.Metal-sulfur interactions,recently,have attracted considerable attention,and there have been new insights on pathways to high‐performance RT-Li/Na sulfur batteries,due to the following factors:(1)deliberate construction of metal-sulfur interactions can enable a leap in capacity;(2)metal-sulfur interactions can confine S species,as well as sodium sulfide compounds,to stop shuttle effects;(3)traces of metal species can help to encapsulate a high loading mass of sulfur with high‐cost efficiency;and(4)metal components make electrodes more conductive.In this review,we highlight the latest progress in sulfide immobilization via constructing metal bonding between various metals and S cathodes.Also,we summarize the storage mechanisms of Li/Na as well as the metal-sulfur interaction mechanisms.Furthermore,the current challenges and future remedies in terms of intact confinement and optimization of the electrochemical performance of RT-Li/Na sulfur systems are discussed in this review.

First-Principles Study of Lithium and Sodium Atoms Intercalation in Fluorinated Graphite

The structure evolution of fluorinated graphite （CFx） upon the Li/Na intercalation has been studied by first- principles calculations. The Li/Na adsorption on single CF layer and intercalated into bulk CF have been calculated. The better cycling performance of Na intercalation into the CF cathode, comparing to that of Li intercalation, is attributed to the different strength and characteristics of the Li-F and Na-F interactions. The interactions between Li and F are stronger and more localized than those between Na and E The strong and localized Coulomb attraction between Li and F atoms breaks the C-F bonds and pulls the F atoms away, and graphene sheets are formed upon Li intercalation.

The application of carbon materials in nonaqueous Na‐O2 batteries

Na‐O2 batteries are advantageous as the candidates of next‐generation electric vehicles due to their ultrahigh theoretical energy density and have attracted enormous attention recently.Tremendous efforts have been devoted to improve the Na‐O2 battery performance by designing advanced electrodes with various carbonbased materials.Carbon materials used in Na‐O2 batteries not only function as the air electrode to provide active sites and accommodate discharge products but also as Na anode protectors against dendrite growth and chemical/electrochemical corrosion.In this review,we mainly focus on the application of various carbonbased materials in Na‐O2 batteries and highlight their advances.The scientific understanding on the fundamental design of the material microstructure and chemistry in relation to the battery performance are summarized.Finally,perspectives on enhancing the overall battery performance based on the optimization and rational design of carbon‐based cell components are also briefly anticipated.

Pressureless all-solid-state Na/S batteries with self-supporting Na_(5)YSi_(4)O_(12) scaffolds

The development of reliable and affordable all-solid-state sodium metal batteries(ASS-SMBs)requires suitable solid-state electrolytes with cost-efficient processing and stabilized electrode/electrolyte interfaces.Here,an integrated porous/dense/porous Na_(5)YSi_(4)O_(12)(NYS)trilayered scaffold is designed and fabricated by tape casting using aqueous slurries.In this template-based NYS scaffold,the dense layer in the middle serves as a separator and the porous layers on both sides accommodate the active materials with their volume changes during the charge/discharge processes,increasing the contact area and thus enhancing the utilization rate and homogenizing the current distribution.The Na/NYS/Na symmetric cells with the Pb-coated NYS scaffold exhibit significantly reduced interfacial impedance and superior critical current density of up to 3.0 mA cm^(-2)against Na metal owing to enhanced wettability.Furthermore,the assembled Na/NYS/S full cells operated without external pressure at room temperature showed a high initial discharge capacity of 970 mAh g^(-1)and good cycling stability with a capacity of 600 mAh g^(-1)after 150 cycles(based on the mass of sulfur).This approach paves the way for the realization of economical and practical ASS-SMBs from the perspective of ceramic manufacturing.

In‐situ structural characterizations of electrochemical intercalation of graphite compounds

Graphite carbon has been successfully used for the anode materials of secondary ion batteries due to its capability of accommodating ions between graphite layers.The intercalation dynamics intrinsically determine the performance of the batteries.In this review,we summarize recent research progresses of structural characterizations on graphite intercalation in electrochemical devices,especially on the in‐situ study on the intercalations of Li/Na/K ions,AlCl4−and other anions,or solvents.These techniques,including X‐ray,electron microscopy,Raman,neutron scattering,nuclear magnetic resonance,and optical microscopy provide direct information of the reaction dynamics and help to understand the factors affecting the electrochemical performances of metallic ion batteries.

Cationic potential:An effective descriptor for rational design of layered oxides for sodium-ion batteries

Sodium-ion batteries are very promising in large-scale energy storage.The exploration of Na layered oxides as cathode materials for Na ion batteries usually consumes much resource,while the performances of Na layered oxides are dominated by their crystal structures.Therefore,it is highly desired to predict the stacking mode of the target oxides in advance:whether O3-type with higher ordered structure and stability,or P2-type with more Na content.For this purpose density functional theory computations do not work.Very recently,Hu's group and international collaborators have proposed a cationic potential to provide a very timely,effective,and accurate criterion to predict the stacking mode of Na layered oxides(Science,370(2020)708-711).Under the guidance of the cationic potential phase map,Na layered oxides could be rationally designed.Here we would like to highlight the progress that novel Na layered oxides could be obtained with the combination of large specific capacity,high power density and good cycling stability.

Stable sodium metal anode enabled by interfacial room-temperature liquid metal engineering for high-performance sodium–sulfur batteries with carbonate-based electrolyte

Sodium(Na)metal is a competitive anode for next-generation energy storage applications in view of its low cost and high-energy density.However,the uncontrolled side reactions,unstable solid electrolyte interphase(SEI)and dendrite growth at the electrode/electrolyte interfaces impede the practical application of Na metal as anode.Herein,a heterogeneous Na-based alloys interfacial protective layer is constructed in situ on the surface of Na foil by self-diffusion of liquid metal at room temperature,named“HAIP Na.”The interfacial Na-based alloys layer with good electrolyte wettability and strong sodiophilicity,and assisted in the construction of NaF-rich SEI.By means of direct visualization and theoretical simulation,we verify that the interfacial Na-based alloys layer enabling uniform Na^(+)flux deposition and suppressing the dendrite growth.As a result,in the carbonate-based electrolyte,the HAIP Na||HAIP Na symmetric cells exhibit a remarkably enhanced cycling life for more than 650 h with a capacity of 1mAh cm^(−2)at a current density of 1mAcm^(−2).When the HAIP Na anode is paired with sulfurized polyacrylonitrile(SPAN)cathode,the SPAN||HAIP Na full cells demonstrate excellent rate performance and cycling stability.

Flexible Na batteries

Flexible energy storage devices have gained significant attention because of the increasing needs of bendable displays,wearable electronics,and flexible displays.Flexible Na-based rechargeable batteries are the promising power sources in such products due to their low cost and wide availability.In this review,we firstly introduce the structural superiority of flexible Na-based batteries and summarize their main components including cathodes,electrolytes,and anodes.Moreover,fabrication of their flexible components is discussed in detail,with specific emphasis on material selection,particularly for solid-state electrolytes.This is followed by an overview highlighting recent progress in the development of prototypes of flexible Na-ion batteries and beyond.Finally,perspectives on future challenges for the development of flexible Na batteries are proposed.

Ultrathin MoS2 with expanded interlayers supported on hierarchical polypyrrole-derived amorphous N-doped carbon tubular structures for high-performance Li/Na-ion

Layered molybdenum disulfide （MoS2） has received much attention as one of the most promising energy-storage and conversion materials for Li/Na ion batteries. Here, a simple and effective approach is proposed for the rational design and preparation of hierarchical three-d imensional （3D） amorphous N-doped carbon nanotube@MoS2 nanosheets （3D-ANCNT@MoS2） via a simple hydrothermal method, followed by an annealing process. With such a unique nanoarchitecture, ultrathin MoS2 nanosheets grown on the external surfaces of polypyrrole-derived ANCNTs are assembled to form a hierarchical 3D nanoarchitecture, where the adopted ANCNTs serve not only as the template and continuous conductive matrix, but can also prevent MoS2 from aggregating and restacking, and help to buffer the volumetric expansion of MoS2 during cycling. More importantly, when evaluated as an anode material for lithium-ion batteries, the 3D-ANCNT@MoS2 composite exhibits excellent cycling stability, superior rate performance, and reversible specific capacity as high as 893.4 mAh·g^-1 at 0.2 A·g^-1 after 200 cycles in a half battery, and 669.4 mAh·g^-1 at 0.2 A·g^-1 after 100 cycles in the 3D-ANCNT@Mo2//LiCoO2 full battery. With respect to sodium-ion batteries, the outstanding reversible capacity, excellent rate behavior, and good cycling performance of 3D-ANCNT@MoS2 composites are also achieved.

Rooting Zn into metallic Na bulk for energetic metal anode

Metallic Na with high theoretical capacity and low redox potential is an attractive anode material for highenergy rechargeable metal batteries.The poor wettability of Na on current collectors and the weak interaction between Na atoms lead to uneven plating/stripping of Na and dendrite formation.Here,we report an encouraging strategy to tackle these issues by rooting Zn into metallic Na bulk through a molten infusion process.The introduction of Zn not only tunes molten Na into highly sodiophilic Na(Zn)but also guides the uniform nucleation of Na through a much stronger interaction.As a result,smooth Na plating and stripping with a low energy barrier and homogeneous current distribution are simultaneously accomplished.Stable galvanostatic cycling over 3000 h in symmetric Na(Zn)cells and low voltage hysteresis below 15 mV at a rate of 5 mA cm^(-2) have been recorded.When coupled with a Na_(3)V_(2)(PO_(4))_(2)O_(2)F cathode,the Na(Zn)-Na_(3)V_(2)(PO_(4))_(2)O_(2)F full cell demonstrates an energetic performance,highlighting the strategy of rooting Zn into alkali metal bulk for rechargeable metal batteries.

Enhancing electrochemical performances of small quinone toward lithium and sodium energy storage

Further application of organic quinone cathodes is restricted because they are inherent in poor conductivity and tend to dissolve in aprotic electrolytes.Salinization can work on the strong solubility of quinones.Herein,the ortho-disodium salt of tetrahydroxyquinone(o-Na_(2)THBQ)was selected to promote the electrochemical properties of tetrahydroxyquinone(THBQ).Reduced dissolution of o-Na_(2)THBQ in electrolyte after salinization(replacement of two H with two Na)contributed to enhanced electrochemical performance.In sodium-ion batteries(SIBs)in ester-based electrolyte,o-Na2THBQ cathodes at 50 mA·g^(-1)exhibited a reversible discharge capacity of 107 mAh·g^(-1)after 200 cycles.Ulteriorly,in ether-based electrolyte,reversible discharge capacities of 200.4,102.2,99.5 and 88 mAh·g^(-1)were obtained at 800,1600,3200 and 4800 mA·g^(-1)after 1000,2000,5000 and 8000 cycles,respectively.The ultraviolet absorption spectra and ex situ dissolution experiments of THBQ and o-Na_(2)THBQ showed that o-Na_(2)THBQ hardly dissolved in ether-based electrolyte.In lithium-ion batteries(LIBs),graphene was selected to further enhance the conductivity of o-Na2THBQ.At 50 mA·g^(-1),o-Na_(2)THBQ and o-Na_(2)THBQ/Gr cathodes exhibited reversible discharge capacities of 124 and 131.5 mAh·g^(-1)after 200 cycles in ester-based electrolyte,respectively.At 50 mA·g^(-1),PTPAn/o-Na_(2)THBQ electrodes in an all-organic Na/Li-ion battery showed reversible charge/discharge capacities of 51/50.3 and 33.8/33.1 mAh·g^(-1)after 200 cycles.

The electrochemical performance of super P carbon black in reversible Li/Na ion uptake

Super P carbon black (SPCB) has been widely used as a conducting additive in Li/Na ion batteries to improve the electronic conductivity. However, there has not yet been a comprehensive study on its structure and electrochemical properties for Li/Na ion uptake, though it is important to characterize its contribution in any study of active materials that uses this additive in non-negligible amounts. In this article the structure of SPCB has been characterized and a comprehensive study on the electrochemical Li/Na ion uptake capability and reaction mechanisms are reported. SPCB exhibits a considerable lithiation capacity (up to 310 mAh g^(–1)) from the Li ion intercalation in the graphite structure. Sodiation in SPCB undergoes two stages: Na ion intercalation into the layers between the graphene sheets and the Na plating in the pores between the nano-graphitic domains, and a sodiation capacity up to 145 mAh g^(–1) has been achieved. Moreover, the influence of the type and content of binders on the lithiation and sodiation properties has been investigated. The cycling stability is much enhanced with sodium carboxymethyl cellulose (NaCMC) binder in the electrode and fluoroethylene carbonate (FEC) in the electrolyte; and a higher content of binder improves the Coulombic efficiency during dis-/charge.