Spherical Shell with CNTs Network Structuring Fe-Based Alluaudite Na2+2 δ Fe2- δ (SO4 )3 Cathode and Novel Phase Transition Mechanism for Sodium-Ion Battery.

Iron-based sulfate cathodes of alluaudite Na2+2 δ Fe2- δ (SO4 )3 (NFS) in sodium-ion batteries with low cost, steady cycling performance, and high voltage are promising for grid-scale energy storage systems. However, the poor electronic conductivity and the limited understanding of the phase-evolution of precursors hinder obtaining high-rate capacity and the pure phase. Distinctive NFS@C@n%CNTs (n = 1, 2, 5, 10) sphere-shell conductive networks composite cathode materials are constructed creatively, which exhibit superior reversible capacity and rate performance. In detail, the designed NFS@C@2%CNTs cathode delivers an initial discharge capacity of 95.9 mAh g-1 at 0.05 C and up to 60 mAh g-1 at a high rate of 10 C. The full NFS@C@2%CNTs//HC cell delivers a practical operating voltage of 3.5 V and mass-energy density of 140 Wh kg-1 at 0.1 C, and it can also retain 67.37 mAh g-1 with a capacity retention rate of 96.4% after 200 cycles at 2 C. On the other hand, a novel combination reaction mechanism is first revealed for forming NFS from the mixtures of Na2 Fe(SO4 )2 ·nH2 O (n = 2, 4) and FeSO4 ·H2 O during the sintering process. The inspiring results would provide a novel perspective to synthesize high-performance alluaudite sulfate and analogs by aqueous methods.

Toward Ultrastable Metal Anode/Li6PS5Cl Interface via an Interlayer as Li Reservoir.

All-solid-state sulfide-based Li metal batteries are promising candidates for energy storage systems. However, thorny issues associated with undesired reactions and contact failure at the anode interface hinder their commercialization. Herein, an indium foil was endowed with a formed interlayer whose surface film is enriched with LiF and LiIn phases via a feasible prelithiation route. The lithiated alloy of the interlayer can regulate Li+ flux and charge distribution as a Li reservoir, benefiting uniform Li deposition. Meanwhile, it can suppress the reductive decomposition of the Li6PS5Cl electrolyte and maintain sufficient solid-solid contact. In situ impedance spectra reveal that constant interface impedance and fast charge transfer are realized by the interlayer. Further, long-term Li stripping/plating over 2000 h at 2.55 mA cm-2 is demonstrated by this anode. All-solid-state cells employing a LiCoO2 cathode and the Pre In anode can work for over 700 cycles with a capacity retention of 96.15% at 0.5 C.

Preparation of Buffered Nano-Submicron Hierarchical Structure Hollow SiOx @C Anodes for Lithium-Ion Battery Materials with Carboxymethyl Chitosan.

Silicon-based materials are among the most promising anode materials for next-generation lithium-ion batteries. However, the volume expansion and poor conductivity of silicon-based materials during the charge and discharge process seriously hinder their practical application in the field of anodes. Here, we choose carboxymethyl chitosan (CMCS) as the carbon source coating and binding on the surface of nano silicon and hollow silicon dioxide (H-SiO2 ) to form a hierarchical buffered structure of nano-hollow SiOx @C. The hollow H-SiO2 can alleviate the volume expansion of nano silicon during the lithiation process under continuous cycling. Meanwhile, the carbon layer carbonized by CMCS containing N-doping further regulates the silicon's expansion and improves the conductivity of the active materials. The as- prepared SiOx @C material exhibits an initial discharge capacity of 985.4 mAh g-1 with the decay rate of 0.27 % per cycle in 150 cycles under the current density of 0.2 A g-1 . It is proved that the hierarchical buffer structure nano-hollow SiOx @C anode material has practical application potential.

Electrochemical Performances of Nickel-Rich Single-Crystal LiNi0.83 Co0.12 Mn0.05 O2 Cathode Material for Lithium-Ion Batteries Synthesized by Tuning Li+ /Ni2+ Mixing.

Single-crystal nickel-rich materials are promising alternatives to polycrystalline cathodes owing to their excellent structure stability and cycle performance while the cathode material usually appears high cation mixing, which may have a negative effect on its electrochemical performance. The study presents the structural evolution of single-crystal LiNi0.83 Co0.12 Mn0.05 O2 in the temperature-composition space using temperature-resolved in situ XRD and the cation mixing is tuned to improve electrochemical performances. The as-synthesized single-crystal sample shows high initial discharge specific capacity (195.5 mAh g-1 at 1 C), and excellent capacity retention (80.1 % after 400 cycles at 1 C), taking account of lower structure disorder (Ni2+ occupying Li sites is 1.56 %) and integrated grains with an average of 2-3 µm. In addition, the single-crystal material also displays a superior rate capability of 159.1 mAh g-1 at the rate of 5 C. This excellent performance is attributed to the rapid Li+ transportation within the crystal structure with fewer Ni2+ cations in Li layer as well as intactly single grains. In sum, the regulation of Li+ /Ni2+ mixing provides a feasible strategy for boosting single-crystal nickel-rich cathode material.

Chemically Induced Activity Recovery of Isolated Lithium in Anode-free Lithium Metal Batteries.

The anode-free lithium metal battery is considered to be an excellent candidate for the new generation energy storage system because of its higher energy density and safety than the traditional lithium metal battery. However, the continuous generation of SEI or isolated Li hinders its practical application. In general, the isolated Li is considered electrochemically inactive because it loses electrical connection with the current collector. Here we show an abnormal phenomenon that the lost capacity appears to be recovered after cycles when the isolated Li reconnects with a deposited Li metal layer. The isolated Li reconnection is ascribed to the chemical induction of the block copolymer coating. The migration of Li+ is affected by the electron delocalization and the electron cloud density of the polymer, which determine the conversion direction of Li+. Based on the mechanism, we propose a strategy to slow down the capacity decay of the anode-free lithium metal battery.

Construction of a N,P doped 3D dendrite-free lithium metal anode by using silicon-containing lithium metal.

Lithium is thought to be an excellent anode material for next-generation Li metal batteries (LMBs). However, some problems with lithium anodes often lead to serious safety concerns and catastrophic failures due to the huge volume change, Li dendritic growth, and related side reactions. Therefore, in order to manufacture stable rechargeable batteries, the abovementioned serious problems must be effectively solved. In this paper, a three-dimensional N,P-doped silicon-containing lithium anode is designed and prepared by in situ metallurgy using low-cost Si3N4. The 3D stable composite anode (DLi/LiSix CA) was prepared by adding a small amount of Si3N4 to molten lithium to form N-doped silicon-containing lithium metal which was supported on a polyaniline modified carbon cloth (PMCC). The results show that the DLi/LiSix CA not only has high Li affinity but can also effectively inhibit lithium nucleation and lithium dendritic growth, so as to maintain good structural stability in the process of Li plating/stripping. The new lithium metal anode based on doping and 3D carbon cloth shows good cycling stability and low polarizability in both symmetrical and full cells.

Progress on Fe-Based Polyanionic Oxide Cathodes Materials toward Grid-Scale Energy Storage for Sodium-Ion Batteries.

The development of large-scale energy storage systems (EESs) is pivotal for applying intermittent renewable energy sources such as solar energy and wind energy. Lithium-ion batteries with LiFePO4 cathode have been explored in the integrated wind and solar power EESs, due to their long cycle life, safety, and low cost of Fe. Considering the penurious reserve and regional distribution of lithium resources, the Fe-based sodium-ion battery cathodes with earth-abundant elements, environmental friendliness, and safety appear to be the better substitutes in impending grid-scale energy storage. Compared to the transition metal oxide and Prussian blue analogs, the Fe-based polyanionic oxide cathodes possess high thermal stability, ultra-long cycle life, and adjustable voltage, which is more commercially viable in the future. This review summarizes the research progress of single Fe-based polyanionic and mixed polyanionic oxide cathodes for the potential sodium-ion batteries EESs candidates. In detail, the synthesized method, crystal structure, electrochemical properties, bottlenecks, and optimization method of Fe-based polyanionic oxide cathodes are discussed systematically. The insights presented in this review may serve as a guideline for designing and optimizing Fe-based polyanionic oxide cathodes for coming commercial sodium-ion batteries EESs.

Thermochemical Cyclization Constructs Bridged Dual-Coating of Ni-Rich Layered Oxide Cathodes for High-Energy Li-Ion Batteries.

Enhancing microstructural and electrochemical stabilities of Ni-rich layered oxides is critical for improving the safety and cycle-life of high-energy Li-ion batteries. Here we propose a thermochemical cyclization strategy where heating polyacrylonitrile with LiNi0.8Co0.1Mn0.1O2 can simultaneously construct a cyclized polyacrylonitrile outer layer and a rock-salt bridge-like inner layer, forming a compact dual-coating of LiNi0.8Co0.1Mn0.1O2. Systematic studies demonstrate that the mild cyclization reaction between polyacrylonitrile and LiNi0.8Co0.1Mn0.1O2 induces a desirable "layered to rock-salt" structural transformation to create a nano-intermedium that acts as the bridge for binding cyclized polyacrylonitrile to layered LiNi0.8Co0.1Mn0.1O2. Because of the improvement of the structural and electrochemical stability and electrical properties, this cathode design remarkably enhances the cycling performance and rate capability of LiNi0.8Co0.1Mn0.1O2, showing a high reversible capacity of 183 mAh g-1 and a high capacity retention of 83% after 300 cycles at 1 C rate. Notably, this facile and scalable surface engineering makes Ni-rich cathodes potentially viable for commercialization in high-energy Li-ion batteries.

Lithium Nitrate Regulated Sulfone Electrolytes for Lithium Metal Batteries.

The electrolytes in lithium metal batteries have to be compatible with both lithium metal anodes and high voltage cathodes, and can be regulated by manipulating the solvation structure. Herein, to enhance the electrolyte stability, lithium nitrate (LiNO3 ) and 1,1,2,2-tetrafuoroethyl-2',2',2'-trifuoroethyl(HFE) are introduced into the high-concentration sulfolane electrolyte to suppress Li dendrite growth and achieve a high Coulombic efficiency of >99 % for both the Li anode and LiNi0.8 Mn0.1 Co0.1 O2 (NMC811) cathodes. Molecular dynamics simulations show that NO3 - participates in the solvation sheath of lithium ions enabling more bis(trifluoromethanesulfonyl)imide anion (TFSI- ) to coordinate with Li+ ions. Therefore, a robust LiNx Oy -LiF-rich solid electrolyte interface (SEI) is formed on the Li surface, suppressing Li dendrite growth. The LiNO3 -containing sulfolane electrolyte can also support the highly aggressive LiNi0.8 Mn0.1 Co0.1 O2 (NMC811) cathode, delivering a discharge capacity of 190.4 mAh g-1 at 0.5 C for 200 cycles with a capacity retention rate of 99.5 %.

A theoretical study on Na+ solvation in carbonate ester and ether solvents for sodium-ion batteries.

The electrochemical performance of sodium-ion batteries is strongly related to the electrolyte solvents. Na+ solvation in commonly used carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) as well as in ether solvents such as 1,3-dioxolane (DOL), tetrahydrofuran (THF), and dimethoxyethane (DME) is studied by the density functional theory for sodium-ion batteries. It is indicated that the thermodynamic equilibrium is reached when forming 4sol-Na+ in the EC, PC, DMC, EMC, DEC, and THF solvents by spontaneous stepwise solvation reactions, and the formation of 3sol-Na+ complexes will reach thermodynamic equilibrium in DOL and DME at room temperature. It is demonstrated that Na+ is more easily solvated by the carbonate ester-based solvents EC, PC, DEC, DMC and EMC compared with that for the ether-based solvents DOL, THF and DME. In addition, the cyclic carbonate ester solvents more easily form a solvation-Na+ complex compared with the linear carbonate ester solvents, and THF is the easiest to form the solvation-Na+ complex among the three ether-based solvents. It is also indicated that the C[double bond, length as m-dash]O and carbonate C-O bond stretching vibrations in carbonate ester solvation complexes move to higher and lower frequencies, respectively, with the decrease in Na+ concentration. In addition, the C-O stretching vibrations with or without Na+ interactions in the ether solvation complexes shift to higher and lower frequencies, respectively, and the shift in frequency is not obvious after forming the maximum innermost solvation shell.

Microsphere-Like SiO2 /MXene Hybrid Material Enabling High Performance Anode for Lithium Ion Batteries.

To address the non-negligible volume expansion and the inherent poor electronic conductivity of silica (SiO2 ) material, microsphere-like SiO2 /MXene hybrid material is designed and successfully synthesized through the combination of the Stöber method and spray drying. The SiO2 nanoparticles are firmly anchored on the laminated MXene by the bonding effect, which boosts the structural stability during the long-term cycling process. The MXene matrix not only possesses high elasticity to buffer the volume variation of SiO2 nanoparticles, but also promotes the transfer of electrons and lithium ions. Moreover, the microsphere wrapped with ductile MXene film reduces the specific surface area, relieves the side reactions, and enhances the coulombic efficiency. Therefore, superior electrochemical performance including high reversible capacity, outstanding cycle stability, high coulombic efficiency, especially in the first cycle, excellent rate capability as well as high areal capacity are acquired for SiO2 /MXene microspheres anode.

Inducing Favorable Cation Antisite by Doping Halogen in Ni-Rich Layered Cathode with Ultrahigh Stability.

The cation antisite is the most recognizable intrinsic defect type in nickel-rich layered and olivine-type cathode materials for lithium-ion batteries, and important for electrochemical/thermal performance. While how to generate the favorable antisite has not been put forward, herein, by combining first-principles calculation with neutron powder diffraction (NPD) study, a defect inducing the favorable antisite mechanism is proposed to improve cathode stability, that is, halogen substitution facilitates the neighboring Li and Ni atoms to exchange their sites, forming a more stable local octahedron of halide (LOSH). According to the mechanism, it is demonstrated by NPD that F-doping not only induces the antisite formation in layered LiNi0.85Co0.075Mn0.075O2 (LNCM), but also increases the antisite concentration linearly. F substitution (1%) induces 5.7% antisite, and it displays an excellent capacity retention of 94% at 1 C for 200 cycles under 25 °C, outstanding high temperature cyclability (153.4 mAh·g-1 at 1 C for 120 cycles under 55 °C). The onset decomposition temperature increases by 48 °C. The ultrahigh cycling/thermal stability is attributed to the stronger LOSH, and it keeps the structural integrity after long cycling and develops an electrostatic repulsion force between oxygen layers to increase the lattice parameter c, which benefits Li-ion migration.

Flexible TiO2 /SiO2 /C Film Anodes for Lithium-Ion Batteries.

Flexible TiO2 /SiO2 /C films are prepared by using an electrospinning approach and used as self-supporting electrodes for lithium-ion batteries (LIBs), which exhibit excellent high-rate capability with a capacity of 115.5 mAh g-1 at 8 A g-1 (9.8 C rate) and good storage performance. The LIBs also show high long-term cycling stability of 700 cycles at 200 mA g-1 with a capacity of 380.1 mAh g-1 and a high capacity retention of 88.3 %. Thus, the TiO2 /SiO2 /C films have the potential to serve as electrodes for flexible LIBs, owing to their flexibility and excellent electrochemical performance.

Electrochemical Properties of the LiNi0.6Co0.2Mn0.2O2 Cathode Material Modified by Lithium Tungstate under High Voltage.

An amount (5 wt %) of lithium tungstate (Li2WO4) as an additive significantly improves the cycle and rate performances of the LiNi0.6Co0.2Mn0.2O2 electrode at the cutoff voltage of 4.6 V. The 5 wt % Li2WO4-mixed LiNi0.6Co0.2Mn0.2O2 electrode delivers a reversible capacity of 199.2 mA h g-1 and keeps 73.1% capacity for 200 cycles at 1 C. It retains 67.4% capacity after 200 cycles at 2 C and delivers a discharge capacity of 167.3 mA h g-1 at 10 C, while those of the pristine electrode are only 44.7% and 87.5 mA h g-1, respectively. It is shown that the structure of the LiNi0.6Co0.2Mn0.2O2 cathode material is not affected by mixing Li2WO4. The introduced Li2WO4 effectively restrains the LiPF6 and carbonate solvent decomposition by consuming PF5 at high cutoff voltage, forming a stable cathode/electrolyte interface film with low resistance.

Density Functional Theory Research into the Reduction Mechanism for the Solvent/Additive in a Sodium-Ion Battery.

The solid-electrolyte interface (SEI) film in a sodium-ion battery is closely related to capacity fading and cycling stability of the battery. However, there are few studies on the SEI film of sodium-ion batteries and the mechanism of SEI film formation is unclear. The mechanism for the reduction of ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), ethylene sulfite (ES), 1,3-propylene sulfite (PS), and fluorinated ethylene carbonate (FEC) is studied by DFT. The reaction activation energies, Gibbs free energies, enthalpies, and structures of the transition states are calculated. It is indicated that VC, ES, and PS additives in the electrolyte are all easier to form organic components in the anode SEI film by one-electron reduction. The priority of one-electron reduction to produce organic SEI components is in the order of VC>PC>EC; two-electron reduction to produce the inorganic Na2 CO3 component is different and follows the order of EC>PC>VC. Two-electron reduction for sulfites ES and PS to form inorganic Na2 SO3 is harder than that of carbonate ester reduction. It is also suggested that the one- and two-electron reductive decomposition pathway for FEC is more feasible to produce inorganic NaF components.

Solid-State Li-Ion Batteries Using Fast, Stable, Glassy Nanocomposite Electrolytes for Good Safety and Long Cycle-Life.

The development of safe, stable, and long-life Li-ion batteries is being intensively pursued to enable the electrification of transportation and intelligent grid applications. Here, we report a new solid-state Li-ion battery technology, using a solid nanocomposite electrolyte composed of porous silica matrices with in situ immobilizing Li(+)-conducting ionic liquid, anode material of MCMB, and cathode material of LiCoO2, LiNi1/3Co1/3Mn1/3O2, or LiFePO4. An injection printing method is used for the electrode/electrolyte preparation. Solid nanocomposite electrolytes exhibit superior performance to the conventional organic electrolytes with regard to safety and cycle-life. They also have a transparent glassy structure with high ionic conductivity and good mechanical strength. Solid-state full cells tested with the various cathodes exhibited high specific capacities, long cycling stability, and excellent high temperature performance. This solid-state battery technology will provide new avenues for the rational engineering of advanced Li-ion batteries and other electrochemical devices.

Novel Slurry Electrolyte Containing Lithium Metasilicate for High Electrochemical Performance of a 5 V Cathode.

We report a novel slurry electrolyte with ultrahigh concentration of insoluble inorganic lithium metasilicate (Li2SiO3) that is exploited for lithium ion batteries to combine the merits of solid and liquid electrolytes. The safety, conductivity, and anodic and storage stabilities of the eletrolyte are examined, which are all enhanced compared to a base carbonate electrolyte. The compatibility of the elecrolyte with a LiNi0.5Mn1.5O4 cathode is evaluated under high voltage. A discharge capacity of 173.8 mAh g(-1) is still maintained after 120 cycles, whereas it is only 74.9 mAh g(-1) in the base electrolyte. Additionally, the rate capability of the LiNi0.5Mn1.5O4 cathode is also improved with reduced electrode polarization. TEM measurements indicate that the electrode interface is modified by Li2SiO3 with a thinner solid electrolyte interphase film. Density functional theory computations demonstrate that LiPF6 is stabilized against its decomposition by Li2SiO3. A possible path for the reaction between PF5 and Li2SiO3 is also proposed by deducing the transition states involved in the process using the DFT method.

New synthesis of a Foamlike Fe3O4/C composite via a self-expanding process and its electrochemical performance as anode material for lithium-ion batteries.

A novel foamlike Fe3O4/C composite is prepared via a sol-gel type method with gelatin as the carbon source and ferric nitrate as the iron source, following a postannealing treatment. Its lithium storage properties as anode material for a lithium-ion battery are thoroughly investigated in this work. With the interaction between ferric nitrate and gelatin, the foamlike architecture is attained through a unique self-expanding process. The Fe3O4/C composite possesses abundant porous structure along with highly dispersed Fe3O4 nanocrystal embedment in the carbon matrix. In the constructed architecture, the 3D porous network property ensures electrolyte accessibility; meanwhile, nanosized Fe3O4 promotes lithiation/delithiation, owing to numerous active sites, large electrolyte contact area, and a short lithium ion diffusion path. As a result, this Fe3O4/C composite electrode demonstrates an excellent cycling stability with a reversible capacity of 1008 mA h g(-1) over 400 cycles at 0.2C (1C = 1000 mA g(-1)), as well as a superior rate performance with reversible capacity of 660 and 580 mA h g(-1) at 3C and 5C, respectively.

Enhanced electrochemical performance of ZnO-loaded/porous carbon composite as anode materials for lithium ion batteries.

ZnO-loaded/porous carbon (PC) composites with different ZnO loading amounts are first synthesized via a facile solvothermal method and evaluated for anode materials of lithium ion batteries. The architecture and the electrochemical performance of the as-prepared composites are investigated through structure characterization and galvanostatic charge/discharge test. The ZnO-loaded/PC composites possess a rich porous structure with well-distributed ZnO particles (size range: 30-100 nm) in the PC host. The one with 54 wt % ZnO loading contents exhibits a high reversible capacity of 653.7 mA h g(-1) after 100 cycles. In particular, a capacity of 496.8 mA h g(-1) can be reversibly obtained when cycled at 1000 mA g(-1). The superior lithium storage properties of the composite may be attributed to its nanoporous structure together with an interconnected network. The modified interfacial reaction kinetics of the composite promotes the intercalation/deintercalation of lithium ions and the charge transfer on the electrode. As a result, the enhanced capacity of the composite electrode is achieved, as well as its high rate capability.