Tuning dual-atom mediator toward high-rate bidirectional polysulfide conversion in Li-S batteries

An emerging practice in the realm of Li-S batteries lies in the employment of single-atom catalysts(SACs)as effective mediators to promote polysulfide conversion,but monometallic SACs affording isolated geometric dispersion and sole electronic configuration limit the catalytic benefits and curtail the cell performance.Here,we propose a class of dual-atom catalytic moieties comprising hetero-or homo-atomic pairs anchored on N-doped graphene(NG)to unlock the liquid–solid redox puzzle of sulfur,readily realizing Li-S full cell under high-rate-charging conditions.As for Fe-Ni-NG,in-depth experimental and theoretical analysis reveal that the hetero-atomic orbital coupling leads to altered energy levels,unique electronic structures,and varied Fe oxidation states in comparison with homo-atomic structures(FeFe-NG or Ni-Ni-NG).This would weaken the bonding energy of polysulfide intermediates and thus enable facile electrochemical kinetics to gain rapid liquid-solid Li_(2)S_(4)?Li_(2)S conversion.Encouragingly,a Li-S battery based on the S@Fe-Ni-NG cathode demonstrates unprecedented fast-charging capability,documenting impressive rate performance(542.7 mA h g^(-1)at 10.0 C)and favorable cyclic stability(a capacity decay of 0.016%per cycle over 3000 cycles at 10.0 C).This finding offers insights to the rational design and application of dual-atom mediators for Li-S batteries.

Lithiation-induced controllable vacancy engineering for developing highly active Ni_(3)Se_(2) as a high-rate and large-capacity battery-type cathode in hybrid supercapacitors

The poor rate capability and low capacity are huge barriers to realize the commercial applications of battery-type transition metal compounds(TMCs) cathode.Herein,numerous Se vacancy defects are introduced into the Ni_(3)Se_(2)lamellas by pre-lithiation technique,which can be acted as a novel class of battery-type cathode for hybrid supercapacitors.Appropriately modulating the contents of the preembedded lithium(Li) ions can induce a controllable vacancy content in the series of as-prepared products,effectively endowing a fast reaction kinetic and high activity for the cathode.Benefiting from the distinct design,the optimized cathode(Li2-Ni_(3)Se_(2)) presents a high specific capacity of 236 mA h g^(-1)at1 A g^(-1),importantly,it can still possess 117 mA h g^(-1)when the current density is increased up to 100A g^(-1),exhibiting relatively high rate capability.It is much superior to other battery-type TMC cathodes reported in previous studies.Moreover,the cathode also shows the excellent cycling stability with 92%capacity retention after 3,000 cycles.In addition,a hybrid supercapacitor(HSC) is assembled with the obtained Li2-Ni_(3)Se_(2)as the cathode and active carbon(AC) as the anode,which delivers a high energy density of 77 W h kg^(-1)at 4 kW kg^(-1)and long-term durability(90% capacitance retention after 10,000 cycles).Therefore,the strategy not only provides an effective way to realize the controllable vacancy content in TMCs for achieving high-perfo rmance cathodes for HSC,but also further promotes their large-scale applications in the energy storage fields.

Concise Strategies to Enhance the High-Rate Performance of Li_(3)VO_(4) Anodes:Cl Doping,Carbon Coating,and Spherical Architecture Design

The safe operating voltage and low volume variation of Li_(3)VO_(4)(LVO)make it an ideal anode material for lithium(Li)-ion batteries.However,the insufficient understanding of the inner storage mechanism hinders the design of LVO-based electrodes.Herein,we investigate,for the first time,the Li-ion storage activity in LVO via Cl doping.Moreover,N-doped C coating was simultaneously achieved in the Cl doping process,resulting in synergistically improved reaction kinetics.As a result,the as-prepared Cl-doped Li_(3)VO_(4) coated with N-doped C(Cl-LVO@NC)electrodes deliver a discharge capacity of 884.1 mAh/g after 200 cycles at 0.2 A/g,which is the highest among all of the LVO-based electrodes.The Cl-LVO@NC electrodes also exhibit high-capacity retention of 331.1 mAh/g at 8.0 A/g and full capacity recovery after 5 periods of rate testing over 400 cycles.After 5000 cycles at 4.0 A/g,the discharge capacity can be maintained at 423.2 mAh/g,which is superior to most LVO-based electrodes.The Li-ion storage activity in LVO via Cl doping and significant improvement in the high-rate Li-ion storage reported in this work can be used as references for the design of advanced LVO-based electrodes for high-power applications.

Designing N-doped graphene/ReSe_(2)/Ti_(3)C_(2) MXene heterostructure frameworks as promising anodes for high-rate potassium-ion batteries

Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which otherwise might not be versatile enough to create desired heterostructures and/or form clean interfacial areas for fast transport of K-ions and electrons.Along this line,rate capability/cycling stability of resulting KIBs are greatly handicapped.Herein we present an all-chemical vapor deposition approach to harness the direct synthesis of nitrogen-doped graphene(NG)/rhenium diselenide(ReSe_2)hybrids over three-dimensional MXene supports as superior heterostructure anode material for KIBs.In such an innovative design,1 T'-ReSe2 nanoparticles are sandwiched in between the NG coatings and MXene frameworks via strong interfacial interactions,thereby affording facile K~+ diffusion,enhancing overall conductivity,boosting high-power performance and reinforcing structural stability of electrodes.Thus-constructed anode delivers an excellent rate performance of 138 mAh g^(-1) at 10.0 A g^(-1) and a high reversible capacity of 90 mAh g^(-1) at 5 A g^(-1) after 300 cycles.Furthermore,the potassium storage mechanism has been systematically probed by advanced in situlex situ characterization techniques in combination with first principles computations.

Surface pseudocapacitance of mesoporous Mo_(3)N_(2) nanowire anode toward reversible high-rate sodium-ion storage

Sodium-ion storage devices are highly desirable for large-scale energy storage applications owing to the wide availability of sodium resources and low cost.Transition metal nitrides(TMNs)are promising anode materials for sodium-ion storage,while their detailed reaction mechanism remains unexplored.Herein,we synthesize the mesoporous Mo3N2 nanowires(Meso-Mo_(3)N_(2)-NWs).The sodium-ion storage mechanism of Mo3N2 is systematically investigated through in-situ XRD,ex-situ experimental characterizations and detailed kinetics analysis.Briefly,the Mo_(3)N_(2) undergoes a surface pseudocapacitive redox charge storage process.Benefiting from the rapid surface redox reaction,the Meso-Mo_(3)N_(2)-NWs anode delivers high specific capacity(282 m Ah g^(-1) at 0.1 A g^(-1)),excellent rate capability(87 m Ah g^(-1) at 16 A g^(-1))and long cycling stability(a capacity retention of 78.6%after 800 cycles at 1 A g^(-1)).The present work highlights that the surface pseudocapacitive sodium-ion storage mechanism enables to overcome the sluggish sodium-ion diffusion process,which opens a new direction to design and synthesize high-rate sodiumion storage materials.

Drying-Mediated Self-Assembly of Graphene for Inkjet Printing of High-Rate Micro-supercapacitors

Scalable fabrication of high-rate micro-supercapacitors(MSCs)is highly desired for on-chip integration of energy storage components.By virtue of the special self-assembly behavior of 2D materials during drying thin films of their liquid dispersion,a new inkjet printing technique of passivated graphene micro-flakes is developed to directly print MSCs with 3D networked porous microstructure.The presence of macroscale through-thickness pores provides fast ion transport pathways and improves the rate capability of the devices even with solid-state electrolytes.During multiple-pass printing,the porous microstructure effectively absorbs the successively printed inks,allowing full printing of 3D structured MSCs comprising multiple vertically stacked cycles of current collectors,electrodes,and sold-state electrolytes.The all-solid-state heterogeneous 3D MSCs exhibit excellent vertical scalability and high areal energy density and power density,evidently outperforming the MSCs fabricated through general printing techniques.

Architecture engineering of carbonaceous anodes for high-rate potassium-ion batteries

The limited lithium resource in earth's crust has stimulated the pursuit of alternative energy storage technologies to lithium-ion battery.Potassium-ion batteries(KIBs)are regarded as a kind of promising candidate for large-scale energy storage owing to the high abundance and low cost of potassium resources.Nevertheless,further development and wide application of KIBs are still challenged by several obstacles,one of which is their fast capacity deterioration at high rates.A considerable amount of effort has recently been devoted to address this problem by developing advanced carbonaceous anode materials with diverse structures and morphologies.This review presents and highlights how the architecture engineering of carbonaceous anode materials gives rise to high-rate performances for KIBs,and also the beneficial conceptions are consciously extracted from the recent progress.Particularly,basic insights into the recent engineering strategies,structural innovation,and the related advances of carbonaceous anodes for high-rate KIBs are under specific concerns.Based on the achievements attained so far,a perspective on the foregoing,and proposed possible directions,and avenues for designing high-rate anodes,are presented finally.

Effect of surface treatment on the structure and high-rate dischargeability properties of AB_5-type hydrogen storage alloy

Surface-treated MmNi3.55Co0.75Mn0.4Al0.3 alloy as negative electrode material of nickel-metal hydride battery was employed to improve the high-rate dischargeability. Surface treatment was realized by dipping and stirring the alloy into a HCl aqueous solution with various concentrations at room temperature. The microstructure of the alloy before and after surface treatment was analyzed by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The electrochemical properties before and after surface treatment were compared, and the alloy treated in 0.025 mol/L HCl solution showed the optimal high-rate dischargeability.

Highly active CoP-CO_(2)N confined in nanocarbon enabling efficient electrocatalytic immobilizing-conversion of polysulfide targeting high-rate lithium-sulfur batteries

Lithium-sulfur batteries suffer from poor cycling stability because of the intrinsic shuttling effect of intermediate polysulfides and sluggish reaction kinetics,especially at high rates and high sulfur loading.Herein,we report the construction of a CoP-CO_(2)N@N-doped carbon polyhedron uniformly anchored on three-dimensional carbon nanotubes/graphene(CoP-CO_(2)N@NC/CG)scaffold as a sulfur reservoir to achieve the trapping-diffusion-conversion of polysulfides.Highly active CoP-CO_(2)N shows marvelous catalytic effects by effectively accelerating the reduction of sulfur and the oxidation of Li_(2)S during the discharging and charging process,respectively,while the conductive NC/CG network with massive mesoporous channels ensures fast and continuous long-distance electron/ion transportation.DFT calculations demonstrate that the CoP-CO_(2)N with excellent intrinsic conductivity serves as job-synergistic immobilizing-conversion sites for polysulfides through the formation of P…Li/N…Li and Co…S bonds.As a result,the S@CoP-CO_(2)N@NC/CG cathode(sulfur content 1.7 mg cm^(-2))exhibits a high capacity of988 mAh g^(-1)at 2 C after 500 cycles,which is superior to most of the electrochemical performance reported.Even under high sulfur content(4.3 mg cm^(-2)),it also shows excellent cyclability with high capacity at 1 C.

Facile synthesis of sulfurized polyacrylonitrile composite as cathode for high-rate lithium-sulfur batteries

Sulfurized polyacrylonitrile(SPAN)as a promising cathode material for lithium sulfur(Li-S)batteries has drawn increasing attention for its improved electrochemical performance in carbonate-based electrolyte.However,the relatively poor electronic and ionic conductivities of SPAN limit its high-rate and lowtemperature performances.In this work,a novel one-dimensional nanofiber SPAN(SFPAN)composite is developed as the cathode material for Li-S batteries.Benefitting from its one-dimensional nanostructure,the SFPAN composite cathode provides fast channels for the migration of ions and electronics,thus effectively improving its electrochemical performance at high rates and low temperature.As a result,the SFPAN maintains a high reversible specific capacity^1200 mAh g−1 after 400 cycles at 0.3 A g−1 and can deliver a high capacity of^850 mAh g−1 even at a high current density of 12.5 A g−1.What is more,the SFPAN can achieve a capacity of^800 mAh g−1 at 0℃and^1550 mAh g−1 at 60℃,thus providing a wider temperature range of applications.This work provides new perspectives on the cathode design for high-rate lithium-sulfur batteries.

High power nano-LiMn_2O_4 cathode materials with high-rate pulse discharge capability for lithium-ion batteries

Nano-LiMn2O4 cathode materials with nano-sized particles are synthesized via a citric acid assisted sol-gel route. The structure, the morphology and the electrochemical properties of the nano-LiMn204 are investigated. Compared with the micro-sized LiMn2O4, the nano-LiMn2O4 possesses a high initial capacity （120 mAh/g） at a discharge rate of 0.2 C （29.6 mA/g）. The nano-LiMn2O4 also has a good high-rate discharge capability, retaining 91% of its capacity at a discharge rate of 10 C and 73~ at a discharge rate of 40 C. In particular, the nano-LiMn2O4 shows an excellent high-rate pulse discharge capability. The cut-off voltage at the end of 50-ms pulse discharge with a discharge rate of 80 C is above 3.40 V, and the voltage returns to over 4.10 V after the pulse discharge. These results show that the prepared nano-LiMn2O4 could be a potential cathode material for the power sources with the capability to deliver very high-rate pulse currents.

Lithium manganese spinel materials for high-rate electrochemical applications

In order to successively compete with supercapacitors, an ability of fast discharge is a must for lithium-ion batteries. From this point of view, stoichiometric and substituted lithium manganese spinels as cathode materials are one of the most prospective candidates, especially in their nanosized form. In this article, an overview of the most recent data regarding physico-chemical and electrochemical properties of lithium manganese spinels, especially, LiMn2O4 and LiNi0.5Mn1.5O4, synthesized by means of various methods is presented, with special emphasis of their use in high-rate electrochemical applications. In particular, specific capacities and rate capabilities of spinel materials are analyzed. It is suggested that reduced specific capacity is determined primarily by the aggregation of material particles, whereas good high-rate capability is governed not only by the size of crystallites but also by the perfectness of crystals. The most technologically advantageous solutions are described, existing gaps in the knowledge of spinel materials are outlined, and the ways of their filling are suggested, in a hope to be helpful in keeping lithium batteries afloat in the struggle for a worthy place among electrochemical energy systems of the 21st century.

Boosting High-Rate Zinc-Storage Performance by the Rational Design of Mn_(2)O_(3) Nanoporous Architecture Cathode

Manganese oxides are regarded as one of the most promising cathode materials in rechargeable aqueous Zn-ion batteries(ZIBs)because of the low price and high security.However,the practical application of Mn2O3 in ZIBs is still plagued by the low specific capacity and poor rate capability.Herein,highly crystalline Mn2O3 materials with interconnected mesostructures and controllable pore sizes are obtained via a ligand-assisted self-assembly process and used as high-performance electrode materials for reversible aqueous ZIBs.The coordination degree between Mn2+and citric acid ligand plays a crucial role in the formation of the mesostructure,and the pore sizes can be easily tuned from 3.2 to 7.3 nm.Ascribed to the unique feature of nanoporous architectures,excellent zinc-storage performance can be achieved in ZIBs during charge/discharge processes.The Mn2O3 electrode exhibits high reversible capacity(233 mAh g−1 at 0.3 A g−1),superior rate capability(162 mAh g−1 retains at 3.08 A g−1)and remarkable cycling durability over 3000 cycles at a high current rate of 3.08 A g−1.Moreover,the corresponding electrode reaction mechanism is studied in depth according to a series of analytical methods.These results suggest that rational design of the nanoporous architecture for electrode materials can effectively improve the battery performance.

Measuring ground deformations caused by 2015 Mw7.8 Nepal earthquake using high-rate GPS data

The April 25, 2015 Mw7.8 Nepal earthquake was successfully recorded by Crustal Movement Observation Network of China （CMONOC） and Nepal Geodetic Array （NGA）. We processed the high-rate GPS data （1 Hz and 5 Hz） by using relative kinematic positioning and derived dynamic ground motions caused by this large earthquake. The dynamic displacements time series clearly indicated the displacement amplitude of each station was related to the rupture directivity. The stations which located in the di- rection of rupture propagation had larger displacement amplitudes than others. Also dynamic ground displacement exceeding 5 cm was detected by the GPS station that was 2000 km away from the epicenter. Permanent coseismic displacements were resolved from the near-field high-rate GPS stations with wavelet decomposition-reconstruction method and P-wave arrivals were also detected with S transform method. The results of this study can be used for earthquake rupture process and Earthquake Early Warning studies.

Focal mechanism inversion of the 2018 M_(W)7.1 Anchorage earthquake based on high-rate GPS observation

The M_(W)7.1 Anchorage earthquake is the most destructive earthquake since the 1964 M_(W)9.2 great Alaska earthquake in the United States.In this study,high-rate GPS data and near-field broadband seismograms are used in separate and joint inversions by the generalized Cut-and-Paste(gCAP)method to estimate the focal mechanism.In order to investigate the influence of crustal velocity structure on the focal mechanism inversion results,two velocity models(Crustl.0 and Alaska Earthquake Center(AEC))are used for detailed comparison and analysis.The results show that:(1)The two nodal planes of the optimal double-couple solution are nearly north-south striking,with dip angles of about 30°and 60°respectively,and the centroid focal depth is 54-55 km,which is an intraplate normal fault event.(2)The inversion results for the two types of data and the two velocity models are consistent with some previous studies,which indicates that the results are stable and reliable.The more accurate velocity structure model is helpful for focal mechanism inversion of the complex earthquake.(3)The inclusion of high-rate GPS data in joint inversion provides a more effective constraint on centroid depth.

Improved High-rate Performance and Cycling Stability of 1D LiFePO_4 Nanorods by a Facile Annealing Process

To alleviate the main limitations of lithium ion diffusion rate and poor electronic conductivity for LiFePO4 cathode material, it is desirable to synthesize nano-size LiFePO4 material due to its enhanced electronic and lithium ion transport rates and thus an improved high-rate performance. However, our previous synthesized LiFePO4 nanorods only exhibited low high-rate and slightly unstable cycle performance. Possible reasons are the poor crystallization and Fe2＋ oxidation of LiFePO4 nanorods prepared by hydrothermal method. In this paper, LiFePO4 nanorods were simply dealt with at 700 ℃ for 4 h under the protection of Ar and H2 mixture gas. The electrochemical properties of LiFePO4/Li cells were investigated by galvanostatic test and cyclic voltammetry（CV）. The experimental results indicated that the annealed LiFePO4 nanorods delivered an excellent cycling stability and obviously improved capacity of 150 mA·h·g-1 at 1C, and even 122 mA·h·g-1 at 5C.

High‑Entropy Layered Oxide Cathode Enabling High‑Rate for Solid‑State Sodium‑Ion Batteries

Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instability,making it difficult to achieve high performance solid-state sodium-ion batteries.Herein,the high-entropy design and Li doping strategy alleviate lattice stress and enhance ionic conductivity,achieving high-rate performance,air stability and electrochemically thermal stability for Na_(0.95)Li_(0.06)Ni_(0.25)Cu_(0.05)Fe_(0.15)Mn_(0.49)O_(2).This cathode delivers a high reversible capacity(141 mAh g^(−1)at 0.2C),excellent rate capability(111 mAh g^(−1)at 8C,85 mAh g^(−1)even at 20C),and long-term stability(over 85%capacity retention after 1000 cycles),which is attributed to a rapid and reversible O3–P3 phase transition in regions of low voltage and suppresses phase transition.Moreover,the compound remains unchanged over seven days and keeps thermal stability until 279℃.Remarkably,the polymer solid-state sodium battery assembled by this cathode provides a capacity of 92 mAh g^(−1)at 5C and keeps retention of 96%after 400 cycles.This strategy inspires more rational designs and could be applied to a series of O3 cathodes to improve the performance of solid-state Na-ion batteries.

GNSS gyroscopes:determination of angular velocity and acceleration with very high-rate GNSS

Although global navigation satellite systems(GNSS)have been routinely applied to determine attitudes,there exists no literature on determining angular velocity and/or angular acceleration from GNSS.Motivated by the invention of computerized accelerometers of the correspondence author and following the success of accurately recovering translational velocity and acceleration waveforms from very high-rate GNSS precise positioning by Xu and his collaborators in 2021,we propose the concept of GNSS gyroscopes and reconstruct angular velocity and acceleration from very high-rate GNSS attitudes by applying regularization under the criterion of minimum mean squared errors.The major results from the experiments can be summarized in the following:(i)angular velocity and acceleration waveforms computed by applying the difference methods to high-rate GNSS attitudes are too noisy and can be physically not meaningful and numerically incorrect.The same can be said about inertial measurement unit(IMU)attitudes,if IMU gyros are not of very high accuracy;(ii)regularization is successfully applied to reconstruct the high-rate angular velocity and acceleration waveforms from 50 Hz GNSS attitudes and significantly outperforms the difference methods,validating the proposed concept of GNSS gyroscopes.By comparing the angular velocity and acceleration results by using the difference methods and regularization,we find that the peak values of angular velocity and acceleration by regularization are much smaller by a maximum factor of 1.57 in the angular velocity to a maximum factor of 8662.53 times in the angular acceleration in the case of high-rate GNSS,and by a maximum factor of 1.26 in the angular velocity to a maximum factor of 2819.85 times in the angular acceleration in the case of IMU,respectively;and(iii)the IMU attitudes apparently lead to better regularized angular velocity and acceleration waveforms than the high-rate GNSS attitudes,which can well be explained by the fact that the former is of better accuracy than the latter.As a result,to suppress the significant amplification of noise in GNSS attitudes,larger regularization parameters have to be chosen for the high-rate GNSS attitudes,resulting in smaller peak angular accelerations by a maximum factor of 37.55 percent in the angular velocity to a maximum factor of 6.20 times in the angular acceleration in comparison of the corresponding IMU results.Nevertheless,the regularized angular acceleration waveforms for both GNSS and IMU look more or less similar in pattern or waveform shape.

Highly-chlorinated inert and robust interphase without mineralization of oxide enhancing high-rate Li metal batteries

Side reactions and dendrite growth triggered by the unstable interface and inhomogeneous deposition have become the biggest obstacle to the commercialization for lithium metal batteries.In this study,a highly-chlorinated organic-inorganic hybrid interfacial protective layer is developed by rationally tuning the interfacial passivation and robustness to achieve the convenient and efficient Li metal anode.The polyvinyl chloride(PVC)can effectively resist water and oxygen,which is confirmed by density functional theory.The organic-dominant solid electrolyte interphases(SEI)with lithium chloride are investigated by the X-ray photoelectron spectroscopy(XPS)with little mineralization of oxide,such as Li_(2)O and Li_(2)CO_(3).With such artificial SEI,a uniform and dense lithium deposition morphology are formed and an ultra-long stable cycle of over 500 h are achieved even at an ultra-high current density of 10 m A/cm^(2).Moreover,the simple and convenient protected anode also exhibits excellent battery stability when paired with the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)and LiFePO_(4)(LFP)cathode,showing great potential for the commercial application of lithium metal batteries.

High-performance magnesium/sodium hybrid ion battery based on sodium vanadate oxide for reversible storage of Na^(+)and Mg^(2+)

Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are an effective way to address these problems.Here,we report a new type of MSHBs that use layered sodium vanadate((Na,Mn)V_(8)O_(20)·5H_(2)O,Mn-NVO)cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide(PTCDI)anode in Mg^(2+)/Na^(+)hybrid electrolytes.During electrochemical cycling,Mg^(2+)and Na^(+)co-participate in the cathode reactions,and the introduction of Na^(+)promotes the structural stability of the Mn-NVO cathode,as cleared by several ex-situ characterizations.Consequently,the Mn-NVO cathode presents great specific capacity(249.9 mA h g^(−1)at 300 mA g^(−1))and cycling(1500 cycles at 1500 mA g^(−1))in the Mg^(2+)/Na^(+)hybrid electrolytes.Besides,full battery displays long lifespan with 10,000 cycles at 1000 mA g^(−1).The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method,and the mechanism for these improvements is discussed.