Photo‑Energized MoS_(2)/CNT Cathode for High‑Performance Li–CO_(2)Batteries in a Wide‑Temperature Range

Li–CO_(2) batteries are considered promising energy storage systems in extreme environments such as Mars;however,severe performance degradation will occur at a subzero temperature owning to the sluggish reaction kinetics.Herein,a photo-energized strategy adopting sustainable solar energy in wide working temperature range Li–CO_(2) battery was achieved with a binder-free MoS_(2)/carbon nanotube(CNT)photo-electrode as cathode.The unique layered structure and excellent photoelectric properties of MoS_(2) facilitate the abundant generation and rapid transfer of photo-excited carriers,which accelerate the CO_(2) reduction and Li_(2)CO_(3) decomposition upon illumination.The illuminated battery at room temperature exhibited high discharge voltage of 2.95 V and mitigated charge voltage of 3.27 V,attaining superior energy efficiency of 90.2%and excellent cycling stability of over 120 cycles.Even at an extremely low temperature of−30℃,the battery with same electrolyte can still deliver a small polarization of 0.45 V by the photoelectric and photothermal synergistic mechanism of MoS_(2)/CNT cathode.This work demonstrates the promising potential of the photo-energized wide working temperature range Li–CO_(2) battery in addressing the obstacle of charge overpotential and energy efficiency.

Recent Advances in Aqueous Zn||MnO_(2)Batteries

Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,achieving high energy density in Zn||MnO_(2)batteries remains challenging,highlighting the need to understand the electrochemical reaction mechanisms underlying these batteries more deeply and optimize battery components,including electrodes and electrolytes.This review comprehensively summarizes the latest advancements for understanding the electrochemistry reaction mechanisms and designing electrodes and electrolytes for Zn||MnO_(2)batteries in mildly and strongly acidic environments.Furthermore,we highlight the key challenges hindering the extensive application of Zn||MnO_(2)batteries,including high-voltage requirements and areal capacity,and propose innovative solutions to overcome these challenges.We suggest that MnO_(2)/Mn^(2+)conversion in neutral electrolytes is a crucial aspect that needs to be addressed to achieve high-performance Zn||MnO_(2)batteries.These approaches could lead to breakthroughs in the future development of Zn||MnO_(2)batteries,off ering a more sustainable,costeff ective,and high-performance alternative to traditional batteries.

The initial stages of Li_(2)O_(2) formation during oxygen reduction reaction in Li-O_(2) batteries:The significance of Li_(2)O_(2) in charge-transfer reactions within devices

Lithium-oxygen batteries are a promising technology because they can greatly surpass the energy density of lithium-ion batteries.However,this theoretical characteristic has not yet been converted into a real device with high cyclability.Problems with air contamination,metallic lithium reactivity,and complex discharge and charge reactions are the main issues for this technology.A fast and reversible oxygen reduction reaction(ORR)is crucial for good performance of secondary batteries',but the partial knowledge of its mechanisms,especially when devices are concerned,hinders further development.From this perspective,the present work uses operando Raman experiments and electrochemical impedance spectroscopy(EIS)to assess the first stages of the discharge processes in porous carbon electrodes,following their changes cycle by cycle at initial operation.A growth kinetic formation of the discharge product signal(Li_(2)O_(2))was observed with operando Raman,indicating a first-order reaction and enabling an analysis by a microkinetic model.The solution mechanism in the evaluated system was ascribed for an equivalent circuit with three time constants.While the time constant for the anode interface reveals to remain relatively constant after the first discharge,its surface seemed to be more non-uniform.The model indicated that the reaction occurs at the Li_(2)O_(2) surface,decreasing the associated resistance during the initial discharge phase.Furthermore,the growth of Li_(2)O_(2) forms a hetero-phase between Li_(2)O_(2)/electrolyte,while creating a more compact and homogeneous on the Li_(2)O_(2)/cathode surface.The methodology here described thus offers a way of directly probing changes in surface chemistry evolution during cycling from a device through EIS analysis.

Plasma-assisted aerogel interface engineering enables uniform Zn^(2+)flux and fast desolvation kinetics toward zinc metal batteries

The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.

Unveiling the tailorable electrochemical properties of zeolitic imidazolate framework-derived Ni-doped LiCoO_(2) for lithium-ion batteries in half/full cells

As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.

Extending the solid solution range of sodium ferric pyrophosphate:Off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)as a novel cathode for sodium‐ion batteries

Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.

In situ observation of the electrochemical behavior of Li–CO_(2)/O_(2)batteries in an environmental transmission electron microscope

Li–CO_(2)/O_(2)batteries,a promising energy storage technology,not only provide ultrahigh discharge capacity but also capture CO_(2)and turn it into renewable energy.Their electrochemical reaction pathways'ambiguity,however,creates a hurdle for their practical application.This study used copper selenide(CuSe)nanosheets as the air cathode medium in an environmental transmission electron microscope to in situ study Li–CO_(2)/O_(2)(mix CO_(2)as well as O_(2)at a volume ratio of 1:1)and Li–O_(2)batteries as well as Li–CO_(2)batteries.Primary discharge reactions take place successively in the Li–CO_(2)/O_(2)–CuSe nanobattery:(I)4Li^(+)+O_(2)+4e^(−)→2Li_(2)O;(II)Li_(2)O+CO_(2)→Li_(2)CO_(3).The charge reaction proceeded via(III)2Li_(2)CO_(3)→4Li^(+)+2CO_(2)+O_(2)+4e^(−).However,Li–O_(2)and Li–CO_(2)nanobatteries showed poor cycling stability,suggesting the difficulty in the direct decomposition of the discharge product.The fluctuations of the Li–CO_(2)/O_(2)battery's electrochemistry were also shown to depend heavily on O_(2).The CuSe‐based Li–CO_(2)/O_(2)battery showed exceptional electrochemical performance.The Li^–CO_(2)/O_(2)battery offered a discharge capacity apex of 15,492 mAh g^(−1) and stable cycling 60 times at 100 mA g^(−1).Our research offers crucial insight into the electrochemical behavior of Li–CO_(2)/O_(2),Li–O_(2),and Li–CO_(2)nanobatteries,which may help the creation of high‐performance Li–CO_(2)/O_(2)batteries for energy storage applications.

Advances in cathode materials for Li-O_(2)batteries

Lithium-oxygen(Li-O_(2))batteries have attracted significant attention due to their ultra-high theoretical energy density.However,serious challenges,such as potential lag,low-rate capability,round-trip efficiency,and poor cycle stability,greatly limit their practical application.This review provides a comprehensive account of the development of Li-O_(2)batteries,elucidates the current discharge/charge mechanism,and highlights both the advantages and bottlenecks of this technology.In particular,recent research progress on various cathode materials,such as carbon-based materials,noble metals,and non-noble metals,for Li-O_(2)batteries is deeply reviewed,emphasizing the impact of design strategies,material structures,chemical compositions,and microphysical parameters on oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)kinetics,as well as discharge products and overall battery performance.This review will also shed light on future research directions for oxygen electrode catalysts and material construction to facilitate the development of Li-O_(2)batteries with maximized electrochemical performance.

One-pot Synthesis of Hierarchical Flower-like WS_(2) Microspheres as Anode Materials for Lithium-ion Batteries

3D hierarchical flowerlike WS_(2) microspheres were synthesized through a facile one-pot hydrothermal route.The as-synthesized samples were characterized by powder X-ray powder diffraction (XRD),energy-dispersive spectroscopy (EDS),scanning electron microscopy (SEM) and Raman.SEM images of the samples reveal that the hierarchical flowerlike WS_(2) microspheres with diameters of about 3-5μm are composed of a number of curled nanosheets.Electrochemical tests such as charge/discharge,cyclic voltammetry,cycle life and rate performance were carried out on the WS_(2) sample.As an anode material for lithium-ion batteries,hierarchical flowerlike WS_(2) microspheres show excellent electrochemical performance.At a current density of100 mA·g^(-1),a high specific capacity of 647.8 mA·h·g^(-1) was achieved after 120 discharge/charge cycles.The excellent electrochemical performance of WS_(2) as an anode material for lithium-ion batteries can be attributed to its special 3D hierarchical structure.

Optimized electrochemical ammonia production:From metal-N_(2)/NO_(x) batteries to aqueous metal-NO_(x)^(–) batteries

Ammonia plays a crucial role in contemporary society,impacting medicine,agriculture,and the chemical industry.The conventional industrial synthesis of NH_(3) through the Haber-Bosch technique,carried out under severe reaction conditions,leads to substantial energy consumption and environmental pollution.It is thus imperative for NH_(3) synthesis methods to be investigated under more favorable conditions.Synthesis of ammonia by electrocatalysis can effectively reduce the environmental damage and other urgent problems,which is a promising solution.Metal-nitrogen series batteries(M-N batteries),such as metal-nitrogen gas batteries,metal-nitrogen oxide batteries and metal-oxynitride batteries have been regarded recently as an exemplar of concurrent NH_(3) synthesis and energy production.Nonetheless,the large-scale application of these batteries is still limited by numerous challenges are currently existing in building high-efficiency M-N batteries,including poor Faradic efficiency and low NH_(3) yield.Therefore,a comprehensive overview of M-N batteries is offered,specifically focusing on advanced strategies for designing highly efficient cathode catalysts in anticipation of future developments.The metal anodes,cathodic electro-reduction reactions,and design principles are encompassed in the discussion,offering detailed insights to enhance understanding.Mechanisms,feasibility analyses,technoeconomic assessments,device combinations,and comparative evaluations are delved into in the review,contributing to a thorough comprehension of diverse systems and their application potential.Perspectives and opportunities for future research directions are also delineated.

Mitigating Lattice Distortion of High‑Voltage LiCoO_(2)via Core‑Shell Structure Induced by Cationic Heterogeneous Co‑Doping for Lithium‑Ion Batteries

Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes.However,the one-step co-doping strategy usually results in small grain size since the low diffusivity ions such as Ti^(4+)will be concentrated on grain boundaries,which hinders the grain growth.In order to synthesize large single-crystal layered oxide cathodes,considering the different diffusivities of different dopant ions,we propose a simple two-step multi-element co-doping strategy to fabricate core–shell structured LiCoO_(2)(CS-LCO).In the current work,the high-diffusivity Al^(3+)/Mg^(2+)ions occupy the core of single-crystal grain while the low diffusivity Ti^(4+)ions enrich the shell layer.The Ti^(4+)-enriched shell layer(~12 nm)with Co/Ti substitution and stronger Ti–O bond gives rise to less oxygen ligand holes.In-situ XRD demonstrates the constrained contraction of c-axis lattice parameter and mitigated structural distortion.Under a high upper cut-off voltage of 4.6 V,the single-crystal CS-LCO maintains a reversible capacity of 159.8 mAh g^(−1)with a good retention of~89%after 300 cycles,and reaches a high specific capacity of 163.8 mAh g^(−1)at 5C.The proposed strategy can be extended to other pairs of low-(Zr^(4+),Ta^(5+),and W6+,etc.)and high-diffusivity cations(Zn^(2+),Ni^(2+),and Fe^(3+),etc.)for rational design of advanced layered oxide core–shell structured cathodes for lithium-ion batteries.

Surface engineering of P2-type cathode material targeting long-cycling and high-rate sodium-ion batteries

The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.

Evolution of the porous structure for phosphoric acid etching carbon as cathodes in Li–O_(2) batteries:Pyrolysis temperature-induced characteristics changes

Although biomass-derived carbon(biochar)has been widely used in the energy field,the relation between the carbonization condition and the physical/chemical property of the product remains elusive.Here,we revealed the carbonization condition's effect on the morphology,surface property,and electrochemical performance of the obtained carbon.An open slit pore structure with shower-puff-like nanoparticles can be obtained by finely tuning the carbonization temperature,and its unique pore structure and surface properties enable the Li–O_(2) battery with cycling longevity(221 cycles with 99.8%Coulombic efficiency at 0.2 mA cm^(−2) and controlled discharge–charge depths of 500 mAh g^(−1))and high capacity(16,334 mAh g^(−1) at 0.02 mA cm^(−2)).This work provides a greater understanding of the mechanism of the biochar carbonization procedure under various pyrolysis conditions,paving the way for future study of energy storage devices.

Sabatier principle guiding the design of cathode catalysts for Li-CO_(2) batteries

The Sabatier principle has been widely used for designing electrocatalysts for energy conversion applications,but it is rarely mentioned in the research of cathode catalyst of Li-CO_(2) batteries.In our work,the"volcanic"relationship between the catalytic activity and the adsorption energy of the catalyst to the intermediates is first demonstrated based on the first-principles calculation,which meets the Sabatier principle and can be used to design the cathode catalysts.The increases in the number of nitrogenvacancy in WN shift the d-band center and increase the interaction with the reactants.The catalytic activity increases first and then decreases with the increase of adsorption energy,which was proved in the experiment.The optimal catalyst for moderate adsorption of intermediate makes the thin LiaCO_(3) distribute evenly.It exhibits a median voltage difference of 0.68 V and an energy efficiency of 84.33%at20μA cm^(-2)with a limited capacity of 200μA h cm^(-2).

Construction of MnS/MoS_(2) heterostructure on two-dimensional MoS_(2) surface to regulate the reaction pathways for high-performance Li-O_(2) batteries

The inherent catalytic anisotropy of two-dimensional(2D) materials has limited the enhancement of LiO_(2) batteries(LOBs) performance due to the significantly different adsorption energies on 2D and edge surfaces.Tuning the adsorption strength in 2D materials to the reaction intermediates is essential for achieving high-performance LOBs.Herein,a MnS/MoS_(2) heterostructure is designed as a cathode catalyst by adjusting the adsorption behavior at the surface.Different from the toroidal-like discharge products on the MoS_(2) cathode,the MnS/MoS_(2) surface displays an improved adsorption energy to reaction species,thereby promoting the growth of the film-like discharge products.MnS can disturb the layer growth of MoS_(2),in which the stack edge plane features a strong interaction with the intermediates and limits the growth of the discharge products.Experimental and theoretical results confirm that the MnS/MoS_(2) heterostructure possesses improved electron transfer kinetics at the interface and plays an important role in the adsorption process for reaction species,which finally affects the morphology of Li_2O_(2),In consequence,the MnS/MoS_(2) heterostructure exhibits a high specific capacity of 11696.0 mA h g^(-1) and good cycle stability over 1800 h with a fixed specific capacity of 600 mA h g^(-1) at current density of100 mA g^(-1) This work provides a novel interfacial engineering strategy to enhance the performance of LOBs by tuning the adsorption properties of 2D materials.

Dual-Functional Electrode Promoting Dendrite-Free and CO_(2) Utilization Enabled High-Reversible Symmetric Na-CO_(2) Batteries

Sodium-carbon dioxide(Na-CO_(2))batteries are regarded as promising energy storage technologies because of their impressive theoretical energy density and CO_(2)reutilization,but their practical applications are restricted by uncontrollable sodium dendrite growth and poor electrochemical kinetics of CO_(2)cathode.Constructing suitable multifunctional electrodes for dendritefree anodes and kinetics-enhanced CO_(2)cathodes is considered one of the most important ways to advance the practical application of Na-CO_(2)batteries.Herein,RuO2 nanoparticles encapsulated in carbon paper(RuCP)are rationally designed and employed as both Na anode host and CO_(2)cathode in Na-CO_(2)batteries.The outstanding sodiophilicity and high catalytic activity of RuCP electrodes can simultaneously contribute to homogenous Na+distribution and dendrite-free sodium structure at the anode,as well as strengthen discharge and charge kinetics at the cathode.The morphological evolution confirmed the uniform deposition of Na on RuCP anode with dense and flat interfaces,delivering enhanced Coulombic efficiency of 99.5%and cycling stability near 1500 cycles.Meanwhile,Na-CO_(2)batteries with RuCP cathode demonstrated excellent cycling stability(>350 cycles).Significantly,implementation of a dendrite-free RuCP@Na anode and catalytic-site-rich RuCP cathode allowed for the construction of a symmetric Na-CO_(2)battery with long-duration cyclability,offering inspiration for extensive practical uses of Na-CO_(2)batteries.

VSe_(2)/V_(2)C heterocatalyst with built-in electric field for efficient lithium-sulfur batteries:Remedies polysulfide shuttle and conversion kinetics

Lithium sulfur(Li-S)battery is a kind of burgeoning energy storage system with high energy density.However,the electrolyte-soluble intermediate lithium polysulfides(Li PSs)undergo notorious shuttle effect,which seriously hinders the commercialization of Li-S batteries.Herein,a unique VSe_(2)/V_(2)C heterostructure with local built-in electric field was rationally engineered from V_(2)C parent via a facile thermal selenization process.It exquisitely synergizes the strong affinity of V_(2)C with the effective electrocatalytic activity of VSe_(2).More importantly,the local built-in electric field at the heterointerface can sufficiently promote the electron/ion transport ability and eventually boost the conversion kinetics of sulfur species.The Li-S battery equipped with VSe_(2)/V_(2)C-CNTs-PP separator achieved an outstanding initial specific capacity of 1439.1 m A h g^(-1)with a high capacity retention of 73%after 100 cycles at0.1 C.More impressively,a wonderful capacity of 571.6 mA h g^(-1)was effectively maintained after 600cycles at 2 C with a capacity decay rate of 0.07%.Even under a sulfur loading of 4.8 mg cm^(-2),areal capacity still can be up to 5.6 m A h cm^(-2).In-situ Raman tests explicitly illustrate the effectiveness of VSe_(2)/V_(2)C-CNTs modifier in restricting Li PSs shuttle.Combined with density functional theory calculations,the underlying mechanism of VSe_(2)/V_(2)C heterostructure for remedying Li PSs shuttling and conversion kinetics was deciphered.The strategy of constructing VSe_(2)/V_(2)C heterocatalyst in this work proposes a universal protocol to design metal selenide-based separator modifier for Li-S battery.Besides,it opens an efficient avenue for the separator engineering of Li-S batteries.

Polypyrrole-coated triple-layer yolk-shell Fe_(2)O_(3)anode materials with their superior overall performance in lithium-ion batteries

Iron oxide(Fe_(2)O_(3))emerges as a highly attractive anode candidate among rapidly expanding energy storage market.Nonethe-less,its considerable volume changes during cycling as an electrode material result in a vast reduced battery cycle life.In this work,an ap-proach is pioneered for preparing high-performance Fe_(2)O_(3)anode materials,by innovatively synthesizing a triple-layer yolk-shell Fe_(2)O_(3)uniformly coated with a conductive polypyrrole(Ppy)layer(Fe_(2)O_(3)@Ppy-TLY).The uniform polypyrrole coating introduces more reac-tion sites and adsorption sites,and maintains structure stability through charge-discharge process.In the uses as lithium-ion battery elec-trodes,Fe_(2)O_(3)@Ppy-TLY demonstrates high reversible specific capacity(maintaining a discharge capacity of 1375.11 mAh·g^(−1)after 500 cycles at 1 C),exceptional cycling stability(retaining the steady charge-discharge performance at 544.33 mAh·g^(−1)after 6000 ultrafast charge-discharge cycles at a 10 C current density),and outstanding high current charge-discharge performance(retaining a reversible ca-pacity of 156.75 mAh·g^(−1)after 10000 cycles at 15 C),thereby exhibiting superior lithium storage performance.This work introduces in-novative advancements for Fe_(2)O_(3)anode design,aiming to enhance its performance in energy storage fields.

Designing ultrastable P2/O3-type layered oxides for sodium ion batteries by regulating Na distribution and oxygen redox chemistry

P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.

Sandwich-type composited solid polymer electrolytes to strengthen the interfacial ionic transportation and bulk conductivity for all-solid-state lithium batteries from room temperature to 120℃

The insurmountable charge transfer impedance at the Li metal/solid polymer electrolytes(SPEs)interface at room temperature as well as the ascending risk of short circuits at the operating temperature higher than the melting point,dominantly limits their applications in solid-state batteries(SSBs).Although the inorganic filler such as CeO_(2)nanoparticle content of composite solid polymer electrolytes(CSPEs)can significantly reduce the enormous charge transfer impedance at the Li metal/SPEs interface,we found that the required content of CeO_(2)nanoparticles in SPEs varies for achieving a decent interfacial charge transfer impedance and the bulk ionic conductivity in CSPEs.In this regard,a sandwich-type composited solid polymer electrolyte with a 10%CeO_(2)CSPEs interlayer sandwiched between two 50%CeO_(2)CSPEs thin layers(sandwiched CSPEs)is constructed to simultaneously achieve low charge transfer impedance and superior ionic conductivity at 30℃.The sandwiched CSPEs allow for stable cycling of Li plating and stripping for 1000 h with 129 mV polarized voltage at 0.1 mA cm^(-2)and 30℃.In addition,the LiFePO_(4)/Sandwiched CSPEs/Li cell also exhibits exceptional cycle performance at 30℃and even elevated120℃without short circuits.Constructing multi-layered CSPEs with optimized contents of the inorganic fillers can be an efficient method for developing all solid-state PEO-based batteries with high performance at a wide range of temperatures.