Li-richening strategy in Li_(2)ZrCl_(6) lattice towards enhanced ionic conductivity

All-solid-state Li batteries(ASSLBs) with solid-state electrolytes(SSEs) are exciting candidates for nextgeneration energy storage and receive considerable attention owing to their reliability. Halide SSEs are promising candidates due to their excellent stability against 4 V-class layered cathodes. Compared with Li3InCl6or Li_(3)ScCl_(6), the low ionic conductivity of Li_(2)ZrCl_(6)(LZC) is a challenge despite its low raw-material cost. Herein, we report a family of Li-Richened chloride, Li_(2+2x)Zr_(1–x)MxCl_(6), which can be used in highperformance ASSLBs owing to its high ionic conductivity(up to 0.62 mS cm^(-1)). The theoretical(ab initio molecular dynamics simulations) and experimental results prove that the strategy of aliovalent substitution with divalent metals to obtain Li-Richened LZC is effective in improving Li^(+)conductivity in SSEs. By combining Li_(2.1)Zr_(0.95)Mg_(0.05)Cl_(6)(Mg5-LZC) with a Li–In anode and a LiCoO_(2)cathode, a room-temperature ASSLBs with excellent long-term cycling stability(88% capacity retention at 0.3C for 100 cycles) and highrate capability(121 m A h g^(-1)at 1C) is reported. This exploratory work sheds light on improving the Li^(+)conductivity of low-cost LZC-family SSEs for constructing high performance ASSLBs.

Cs-Induced Phase Transformation of Vanadium Oxide for High-Performance Zinc-Ion Batteries

Rechargeable aqueous zinc-ion batteries are promising candidate for gridscale energy storage.However,the development of zinc-ion batteries has been plagued by the lack of cathode materials with high specific capacity and superior lifespan.Herein,hexagonal Cs_(0.3)V_(2)O_(5)cathode is fabricated and investigated in zinc-ion batteries.Compared with the traditional vanadium oxides,the introduction of Cs changes the periodic atomic arrangements,which not only stabilizes the open framework structure but also facilitates the Zn^(2+)diffusion with a lower migration energy barrier.Consequently,high specific capacity of 543.8 mA h g^(-1)at 0.1 A g^(-1)is achieved,which surpasses most of reported cathode materials in zinc-ion batteries.The excellent cycle life is achieved over 1000 cycles with about 87.8%capacity retention at 2 A g^(-1).Furthermore,the morphological evolution and energy storage mechanisms are also revealed via a series of techniques.This work opens up a phase engineering strategy to fabricate the hexagonal vanadium oxide and elucidate the application of phase-dependent cathodes in zinc-ion batteries.

Formation of NiFe_2O_4/Expanded Graphite Nanocomposites with Superior Lithium Storage Properties

A Ni Fe_2O_4/expanded graphite(Ni Fe_2O_4/EG)nanocomposite was prepared via a simple and inexpensive synthesis method. Its lithium storage properties were studied with the goal of applying it as an anode in a lithium-ion battery. The obtained nanocomposite exhibited a good cycle performance, with a capacity of 601 m Ah g^(-1)at a current of 1 A g^(-1)after 800 cycles. This good performance may beattributed to the enhanced electrical conductivity and layered structure of the EG. Its high mechanical strength could postpone the disintegration of the nanocomposite structure,efficiently accommodate volume changes in the Ni Fe_2O_4-based anodes, and alleviate aggregation of Ni Fe_2O_4 nanoparticles.

Recent Advances on Porous Materials for Synergetic Adsorption and Photocatalysis

Porous photocatalysts are promising materials capable of simultaneously adsorbing and oxidizing/reducing target species,showing great potentials in environmental remediation and energy generation.This review offered a comprehensive overview of the recent progress in design,fabrication,and applications of porous photocatalysts,including carbon-based semiconductors,metal oxides/sulfides,metal–organic frameworks,and adsorbent–photocatalyst hybrids.The fundamental understanding of the structure–performance relationships of porous materials together with the in-depth insights into the synergetic effects between adsorption and photocatalysis was presented.The strategies to further improve the photocatalytic activity of porous photocatalysts were proposed.This review would provide references and outlooks of constructing efficient porous materials for adsorptive and photocatalytic removal of pollutants and energy production.

Rechargeable Aqueous Zinc-Ion Batteries in MgSO4/ZnSO4 Hybrid Electrolytes

MgSO4 is chosen as an additive to address the capacity fading issue in the rechargeable zinc-ion battery system of MgxV2O5·nH2O//ZnSO4//zinc.Electrolytes with different concentration ratios of ZnSO4 and MgSO4 are investigated.The batteries measured in the 1 M ZnSO4^-1 M MgSO4 electrolyte outplay other competitors,which deliver a high specific capacity of 374 mAh g^-1 at a current density of 100 mA g^-1 and exhibit a competitive rate performance with the reversible capacity of 175 mAh g^-1 at 5 A g^-1.This study provides a promising route to improve the performance of vanadium-based cathodes for aqueous zinc-ion batteries with electrolyte optimization in cost-effective electrolytes.

From protonation & Li-rich contamination to grain-boundary segregation: Evaluations of solvent-free vs. wet routes on preparing Li_(7)La_(3)Zr_(2)O_(12) solid electrolyte

Garnet-type Li_(7)La_(3)Zr_(2)O_(12)(LLZO) has been recognized as a candidate solid electrolyte for high-safety Lianode based solid-state batteries because of its electro-chemical stability against Li-metal and high ionic conductivity. Solvent(e.g., isopropanol(IPA)) has been commonly applied for preparing LLZO powders and ceramics. However, the deterioration of the proton-exchange between LLZO and IPA/absorbed moisture during the mixing and tailoring route has aroused less attention. In this study, a solvent-free dry milling route was developed for preparing the LLZO powders and ceramics. For orthogonal four categories of samples prepared using solvent-free and IPA-assisted routes in the mixing and tailoring processes, the critical evaluation was conducted on the crystallinity, surficial morphology, and contamination of ascalcinated and as-tailored particles, the cross-sectional microstructure of green and sintered pellets,the morphology and electro-chemical properties of grain boundaries in ceramics, as well as the interfacial resistance and performance of Li anode based symmetric batteries. The wet route introduced Li-rich contaminations(e.g., Li OH·H)_(2)O and Li)_(2)CO)_(3)) onto the surfaces of LLZO particles and Li-Ta-O segregations at the adjacent and triangular grain boundaries. The LLZO solid electrolytes prepared through dry mixing in combination with the dry tailoring route without the use of any solvent were found to the optimal performance. The fundamental material properties in the whole LLZO preparation process were found, which are of guiding significance to the development of LLZO powder and ceramic production craft.

Carbon Supported MoO_(2) Spheres Boosting Ultra-Stable Lithium Storage with High Volumetric Density

As important ingredients in lithium-ion battery,the Coulombic efficiency and power density greatly impact the electrochemical performances.Although recent literatures have reported nano-porous materials to enhance the specific capacities,intrinsic drawbacks such as poor initial Coulombic efficiency and low volumetric capacity could not be avoided.Herein,we propose a strategy to prepare carbon supported MoO_(2)spheres used for lithium-ion battery with high volumetric capacity density.A high initial Coulombic efficiency of 76.5%is obtained due to limited solid electrolyte interface film formed on the exposed surface.Meantime,the sample with an optimal carbon content and a proper structural strength reveals a higher reversible capacity of 956 mA h g^(-1)than the theoretical capacity of crystalline Mo O_(2)(838 mA h g^(-1))and a high capacity retention ratio of 96.4%after 100 cycles at 0.5 A g^(-1).And an effective compaction capacity density(under 5 MPa)of 670 mA h cm^(-3)of the spheres proves its potential value in practical applications.

Halide/sulfide composite solid-state electrolyte for Li-anode based all-solid-state batteries

Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-class cathodes and low bill-of-material(BOM) cost.However,despite the benefits,the poor chemical/electrochemical stability of LZC against Li metal causes the deterioration of Li/LZC interface,which has a detrimental inhibition on Li^(+) transport in ASSLBs.Herein,we report a composite SSE combining by LZC and argyrodite buffer layer(Li_(6)PS_(5)Cl,LPSC) that prevent the unfavorable interaction between LZC and Li metal.The Li/LPSC-LZC-LPSC/Li symmetric cell stably cycles for over 1000 h at 0.3 mA/cm^(2)(0.15mAh/cm^(2)) and has a high critical current density(CCD) value of 2.1 mA/cm^(2)at 25 ℃,Under high temperature(60℃) which promotes the reaction between Li and LZC,symmetric cell fabricated with composite SSE also display stable cycling performance over 1200h at 0.3 mAh/cm^(2).Especially,the Li/NCM ASSLBs fabricated with composite SSE exhibit a high initial coulombic efficiency,as well as superior cycling and rate performance.This simple and efficient strategy will be instrumental in the development of halidebased high-performance ASSLBs.

A multiphase sodium vanadium phosphate cathode material for high-rate sodium-ion batteries

The unsatisfactory rate capability and poor cycling stability at high rate of sodium-ion batteries(SIBs) have impeded their practical applications. Herein, a Na_(3)V_(2)(PO_(4))_(3)/Na_(3)V_(3)(PO_(4))_(4) multiphase cathode materials for high-rate and long cycling SIBs was successfully synthesized by regulation the stoichiometric ratio of raw materials. The combined experiment and simulation results show that the multiphase materials consisted of NASICON structural phase Na3V2(PO4)3 and layered structure phase Na_(3)V_(3)(PO_(4))_(4), possess abundant phase boundaries. Electrochemical experiments demonstrate that the multiphase materials maintain a remarkable reversible capacity of 69.0 mA h g^(-1) even at an ultrahigh current density of 100 C with a high capacity retention of 81.25 % even after 10,000 cycles. Na_(3)V_(2)(PO_(4))_(3)/Na_(3)V_(3)(PO_(4))_(4) electrode exhibits a higher working voltage, superior rate capability and better cycling stability than Na_(3)V_(2)(PO_(4))_(3) electrode, which indicates that the introduction of second phase can be an effective strategy for the development of novel cathode materials for SIBs.

Aqueous Zn^(2+)/Na^(+) dual-salt batteries with stable discharge voltage and high Coulombic efficiency by systematic electrolyte regulation

While aqueous Zn-Na hybrid batteries have garnered widespread attention because of their low cost and high safety,it is still challenging to achieve long cycle-life and stable discharge-voltage due to sluggish reaction kinetics,zinc dendrite formation,and side reactions.Herein,we design a Zn^(2+)/Na^(+) dual-salt battery,in which sodiation of the NVP cathode favors zinc intercalation under an energy threshold,leading to decoupled redox reactions on the cathode and anode.Systematic investigations of the electrolyte effects show that the ion intercalation mechanism and the kinetics in the mixture of triflate-and acetate-based electrolytes are superior to those in the common acetate-only electrolytes.As a result,we have achieved fast discharging capability,suppressed zinc dendrites,a stable discharge voltage at 1.45 V with small polarization,and nearly 100%Coulombic efficiency in the dual-salt mixture electrolyte with optimized concentration of 1 M Zn(OAc)_(2)+1 M NaCF_(3)SO_(3).This work demonstrates the importance of electrolyte regulation in aqueous dual-salt hybrid batteries for the energy storage.

Constructing stable Li-solid electrolyte interphase to achieve dendrites-free solid-state battery:A nano-interlayer/Li prereduction strategy

Solid-state batteries based on Li and nonflammable solid-state electrolytes(SSEs)have aroused the attention of numerous researchers because of their absolute safety and potentially high energy density.Most SSEs after coming into contact with Li are reduced,which leads to high interfacial charge-transfer impedance and dendrites formation.In this study,an“interlayer-Li pre-reduction strategy”was proposed to solve the above problem of reduction.An intermediate layer was introduced between solid electrolyte and Li,and it reacted with Li to produce a stable and ion-conductive interphase.Cubic garnet-type Nb-doped Li_(7)La_(3)Zr_(2)O_(12)(Nb-LLZO)was selected as an example solid electrolyte since it is characterized by high ionic conductivity,feasible preparation under ambient conditions,as well as low cost.The high impedance arising from the reduction at the Nb-LLZO|Li interface has limited its application.In this paper,a nano-scale Li phosphorus oxynitride(LiPON)layer was deposited on the Nb-LLZO pellets through radio frequency(RF)magnetron sputtering,which pre-reacted with Li in-situ to produce a lithiophilic,electronically insulating,and ionic conductive interphase.The produced interphase significantly inhibited the reduction of Nb5+against Li and the formation and propagation of Li dendrites.It is noteworthy that Li|LiPON|Nb-LLZO|LiPON|Li cells stably cycled for over 2,000 h without any short circuit.This study emphasizes and demonstrates the significance of the pre-conversion of modification layer between unstable SSE and Li metal to improve interfacial stability.