Stabilizing High-Nickel Cathodes via Interfacial Hydrogen Bonding Effects Using a Hydrofluoric Acid-Scavenging Separator

Nickel-rich layered Li transition metal oxides are the most promising cathode materials for high-energydensity Li-ion batteries.However,they exhibit rapid capacity degradation induced by transition metal dissolution and structural reconstruction,which are associated with hydrofluoric acid(HF)generation from lithium hexafluorophosphate decomposition.The potential for thermal runaway during the working process poses another challenge.Separators are promising components to alleviate the aforementioned obstacles.Herein,an ultrathin double-layered separator with a 10 lm polyimide(PI)basement and a 2 lm polyvinylidene difluoride(PVDF)coating layer is designed and fabricated by combining a nonsolvent induced phase inversion process and coating method.The PI skeleton provides good stability against potential thermal shrinkage,and the strong PI-PVDF bonding endows the composite separator with robust structural integrity;these characteristics jointly contribute to the extraordinary mechanical tolerance of the separator at elevated temperatures.Additionally,unique HF-scavenging effects are achieved with the formation of-CO…H-F hydrogen bonds for the abundant HF coordination sites provided by the imide ring;hence,the layered Ni-rich cathodes are protected from HF attack,which ultimately reduces transition metal dissolution and facilitates long-term cyclability of the Ni-rich cathodes.Li||NCM811 batteries(where“NCM”indicates LiNi_(x)Co_(y)Mn_(1-x-y)O_(2))with the proposed composite separator exhibit a 90.6%capacity retention after 400 cycles at room temperature and remain sustainable at 60℃with a 91.4%capacity retention after 200 cycles.By adopting a new perspective on separators,this study presents a feasible and promising strategy for suppressing capacity degradation and enabling the safe operation of Ni-rich cathode materials.

A Single-Layer Piezoelectric Composite Separator for Durable Operation of Li Metal Anode at High Rates

Piezoelectric ceramic and polymeric separators have been proposed to effectively regulate Li deposition and suppress dendrite growth,but such separators still fail to satisfactorily support durable operation of lithium metal batteries owing to the fragile ceramic layer or low-piezoelectricity polymer as employed.Herein,by combining PVDF-HFP and ferroelectric BaTiO_(3),we develop a homogeneous,single-layer composite separator with strong piezoelectric effects to inhibit dendrite growth while maintaining high mechanical strength.As squeezed by local protrusion,the polarized PVDF-HFP/BaTiO_(3)composite separator generates a local voltage to suppress the local-intensified electric field and further deconcentrate regional lithium-ion flux to retard lithium deposition on the protrusion,hence enabling a smoother and more compact lithium deposition morphology than the unpoled composite separator and the pure PVDF-HFP separator,especially at high rates.Remarkably,the homogeneous incorporation of BaTiO_(3)highly improves the piezoelectric performances of the separator with residual polarization of 0.086 pC cm^(-2)after polarization treatment,four times that of the pure PVDF-HFP separator,and simultaneously increases the transference number of lithium-ion from 0.45 to 0.57.Beneficial from the prominent piezoelectric mechanism,the polarized PVDF-HFP/BaTiO_(3)composite separator enables stable cyclic performances of Li||LiFePO_(4)cells for 400 cycles at 2 C(1 C=170 mA g^(-1))with a capacity retention above 99%,and for 600 cycles at 5 C with a capacity retention over 85%.

利用ToF-SIMS和Rf-GDOES深度剖析技术研究柔性衬底上的隔热多层膜

目的:探究隔热多层膜VG1的层结构和光学性能。方法:利用飞行时间二次离子质谱(Time of Flight Secondary Ion Mass Spectroscopy, ToF-SIMS)和射频辉光放电发射光谱(Radio-Frequency Glow Dis-charge Optical Emission Spectroscopy, Rf-GDOES)深度剖析技术,对PET柔性衬底上的隔热多层膜进行了成分分布和层结构的对比研究。利用Mixing-Roughness-Information (MRI)模型对测量的深度剖析谱进行了定量分析,并利用分光光度计对多层膜的光学性能进行表征。结果:通过深度剖析的定量分析,确定了所研究隔热多层膜主要组成元素的成分随深度变化的分布为:Nb2O5 (~25 nm)/AZO (Ag) (~10 nm)/Nb2O5 (~50 nm)/AZO (Ag) (~10 nm)/Nb2O5 (~25 nm),整个薄膜厚度约为120 nm。利用深度剖析数据拟合获得的粗糙度参数随深度变化的关系,估算出ToF-SIMS和Rf-GDOES深度剖析溅射到第二个Ag峰前界面处的粗糙度分别为1.2 nm和4.6 nm。对透过率的表征发现,该多层膜样品较PET衬底可见光的透过率增加了11%,而红外光的透过率降低了66%。结论:利用Rf-GDOES和ToF-SIMS溅射深度剖析定量分析技术,确定了柔性衬底上隔热功能薄膜的元素成分分布、膜厚及膜层间界面粗糙度,并利用分光光度计定量确定了该隔热功能多层膜的透过率。

Three-Dimensional Cooperative Localization via Space-Air-Ground Integrated Networks

The space-air-ground integrated network(SAGIN)combines the superiority of the satellite,aerial,and ground communications,which is envisioned to provide high-precision positioning ability as well as seamless connectivity in the 5G and Beyond 5G(B5G)systems.In this paper,we propose a three-dimensional SAGIN localization scheme for ground agents utilizing multi-source information from satellites,base stations and unmanned aerial vehicles(UAVs).Based on the designed scheme,we derive the positioning performance bound and establish a distributed maximum likelihood algorithm to jointly estimate the positions and clock offsets of ground agents.Simulation results demonstrate the validity of the SAGIN localization scheme and reveal the effects of the number of satellites,the number of base stations,the number of UAVs and clock noise on positioning performance.

A surfactant-modified composite separator for high safe lithium ion battery

Separators have been gaining increasing attention to improve the performance of lithium ion batteries(LIBs),especially for high safe and long cycle life.However,commercial polyolefin separators still face the problems of rapid capacity decay and safety issues due to the poor wettability with electrolytes and low thermal stability.Herein,a novel composite separator is proposed by introducing a surfactant of sodium dodecyl thiosulfate(SDS)into the polytetrafluoroethylene(PTFE)substrate with the binder of polyacrylic acid(PAA)through the suction filtration method.The introduction of PAA/SDS enhances the adsorption energy between PTFE substrate and electrolyte through density functional theory calculations,which improves wettability and electrolyte uptake of the separator significantly.The asachieved composite separator enables the LIBs to own high Li^(+)conductivity(0.64×10^(-3)S cm^(-1))and Li^(+)transference number(0.63),further leading to a high capacity retention of 93.50%after 500 cycles at 1 C.In addition,the uniform and smooth surface morphology of Li metal employed the composite separator after cycling indicates that the lithium dendrites can be successfully inhibited.This work indicates a promising route for the preparation of a novel composite separator for high safe LIBs.

Flow control performance evaluation of a tri-electrode sliding discharge plasma actuator

Tri-electrode sliding discharge(TED)plasma actuators are formed by adding a direct current(DC)exposed electrode to conventional dielectric barrier discharge(DBD)plasma actuators.There are three TED modes depending on the polarity and amplitude of the DC supply:DBD discharge,extended discharge and sliding discharge.This paper evaluates the electrical,aerodynamic and mechanical characteristics of a TED plasma actuator based on energy analysis,particle image velocimetry experiments and calculations using the Navier-Stokes equation.The flow control performances of different discharge modes are quantitatively analyzed based on characteristic parameters.The results show that flow control performance in both extended discharge and sliding discharge is more significant than that of DBD,mainly because of the significantly higher(up to 141%)body force of TED compared with DBD.However,conductivity loss is the primary power loss caused by the DC polarity for TED discharge.Therefore,power consumption can be reduced by optimizing the dielectric material and thickness,thus improving the flow control performance of plasma actuators.

Electrical and aerodynamic characteristics of sliding discharge based on a microsecond pulsed plasma supply

Plasma flow control technology has broad prospects for application.Compared with conventional dielectric barrier discharge plasma actuators(DBD-PA),the sliding discharge plasma actuator(SD-PA)has the advantages of a large discharge area and a deflectable induced jet.To achieve the basic performance requirements of light weight,low cost,and high reliability required for UAV(Unmanned Aerial Vehicle)plasma flight experiments,this work designed a microsecond pulse plasma supply that can be used for sliding discharge plasma actuators.In this study,the topology of the primary circuit of the microsecond pulse supply is determined,the waveform of the output terminal of the microsecond pulse plasma supply is detected using the Simulink simulation platform,and the design of the actuation voltage,the pulse frequency modulation function and the construction of the hardware circuit are achieved.Using electrical diagnosis and flow field analysis,the actuation characteristics and flow characteristics of sliding discharge plasma under microsecond pulse actuation are studied,the optimal electrical actuation parameters and flow field characteristics are described.

Modification strategies for non-aqueous, highly proton-conductive benzimidazole-based high-temperature proton exchange membranes

High-temperature proton exchange membranes(HT-PEMs) possess excellent thermal and outstanding electrochemical stability, providing an avenue to realize high-temperature proton exchange membranes fuel cells(HT-PEMFCs) with both superior power density and long-term durability. Unfortunately, polybenzimidazole(PBI), a typical material for conventional HT-PEMs, fails to compromise the high nonaqueous proton conductivity and high mechanical properties, thus hindering their practical applications.Achieving efficient nonaqueous proton conduction is crucial for HT-PEMFC, and many insightful research works have been done in this area. However, there still lacks a report that integrates the host-guest interactions of phosphoric acid doping and the structural stability of polymers to systematically illustrate modification strategies. Here, we summarize recent advancements in enhancing the nonaqueous proton conduction of HT-PEMs. Various polymer structure modification strategies, including main chain and side group modification, cross-linking, blocking, and branching, are reviewed. Composite approaches of polymer, including compounding with organic porous polymers, filling the inorganic components and modifying with ionic liquids, etc., are also covered in this work. These strategies endow the HT-PEMs with more free volume, nanophase-separated structure, and multi-stage proton transfer channels, which can facilitate the proton transportation and improve their performance. Finally, current challenges and future directions for further enhancements are also outlined.

Multiparameter performance monitoring of pulse amplitude modulation channels using convolutional neural networks

A designed visual geometry group(VGG)-based convolutional neural network(CNN)model with small computational cost and high accuracy is utilized to monitor pulse amplitude modulation-based intensity modulation and direct detection channel performance using eye diagram measurements.Experimental results show that the proposed technique can achieve a high accuracy in jointly monitoring modulation format,probabilistic shaping,roll-off factor,baud rate,optical signal-to-noise ratio,and chromatic dispersion.The designed VGG-based CNN model outperforms the other four traditional machine-learning methods in different scenarios.Furthermore,the multitask learning model combined with MobileNet CNN is designed to improve the flexibility of the network.Compared with the designed VGG-based CNN,the MobileNet-based MTL does not need to train all the classes,and it can simultaneously monitor single parameter or multiple parameters without sacrificing accuracy,indicating great potential in various monitoring scenarios.

Polybenzimidazole functionalized electrolyte with Li-wetting and self-fluorination functionalities for practical Li metal batteries

Rough Li plating,low ionic conductivity,and low thermal stability of conventional electrolytes post-primary challenges for achieving reliable high-capacity rechargeable lithium batteries,for which lithiummetal is frequently proposed as themost promising anode material.Conventional low-polarity commercial polypropylene/polyethylene separators fail to support the application of high-energy-density Li anodes due to their rigid physicochemical properties and the high reactivity of Li metal,leading to fatal dendrite formation and vigorous exothermic reaction with electrolytes.Herein,we develop a Li-wetting,flame-retardant binary polymer electrolyte by functionalizing poly(vinylidene fluoride)(PVDF)separators with nonflammable polybenzimidazole(PBI)to build safe room-temperature solid-state electrolyte membranes.A dendrite-free LiFePO4 cell with the solid polymer electrolyte(SPE)delivers a discharge capacity of 127 mAh g^(-1) at 25℃ with a capacity retention of 87.5%after 500 cycles at 0.5℃(0.15 mA cm^(-2)).Phase-field simulations and density functional theory calculations demonstrate that the negatively charged benzimidazole chains of PBI own superior affinity to lithium bis(trifluoromethanesulfonyl)imide(LiTFSI),and shares overlapping electron density with Li anode,giving rise to accelerated Li^(+)conduction at room temperature and uniform Li electrodeposition at the electrolyte/Li metal interface.The SPE is also flame-retardant since heat-resistant polytetrafluoroethylene and a dense,heat-blocking graphitized carbon layer are formed in intense heat throughdehydrogenation/fluorination of PVDF under the catalysis of Lewis base imidazole rings and the decomposition of benzimidazole rings in PBI.No such fire-resistant mechanism is ever reported in conventional electrolytes.

A novel inflatable rings supported design and buoyancy-weight balance deformation analysis of stratosphere airships

Owing to the unique advantages in flight altitude,dwelling time and wide coverage area,stratospheric airships provide permanent monitoring and surveillance for both civil and military applications.Here we propose a semi-rigid stratosphere airship design with circumferential high-pressure inflatable rings and a longitudinal carbon fiber skeleton supported inside.We perform numerical simulations to analyze the deformation characteristics during the whole ascending and descending process.An equivalent internal gradient pressure model of helium is established based on the capsule shape and buoyancy-weight equilibrium conditions.The implicit dynamic method is used to deal with the large deformation of the airship capsule under a low negative pressure condition.Deformation and load-bearing performance of the airship capsule,inflatable ring,skeleton,and suspension line are obtained under different working conditions.The results show that the airship,supported with the inflatable rings and the suspension lines,effectively maintains the shape and ensures the stiffness during the ascending,dwelling,and descending stages,especially suffering from negative pressure.

Electrolyte Engineering for High-Voltage Lithium Metal Batteries

High-voltage lithium metal batteries(HVLMBs)have been arguably regarded as the most prospective solution to ultrahigh-density energy storage devices beyond the reach of current technologies.Electrolyte,the only component inside the HVLMBs in contact with both aggressive cathode and Li anode,is expected to maintain stable electrode/electrolyte interfaces(EEIs)and facilitate reversible Li+transference.Unfortunately,traditional electrolytes with narrow electrochemical windows fail to compromise the catalysis of high-voltage cathodes and infamous reactivity of the Li metal anode,which serves as a major contributor to detrimental electrochemical performance fading and thus impedes their practical applications.Developing stable electrolytes is vital for the further development of HVLMBs.However,optimization principles,design strategies,and future perspectives for the electrolytes of the HVLMBs have not been summarized in detail.This review first gives a systematical overview of recent progress in the improvement of traditional electrolytes and the design of novel electrolytes for the HVLMBs.Different strategies of conventional electrolyte modification,including high concentration electrolytes and CEI and SEI formation with additives,are covered.Novel electrolytes including fluorinated,ionic-liquid,sulfone,nitrile,and solid-state electrolytes are also outlined.In addition,theoretical studies and advanced characterization methods based on the electrolytes of the HVLMBs are probed to study the internal mechanism for ultrahigh stability at an extreme potential.It also foresees future research directions and perspectives for further development of electrolytes in the HVLMBs.

Talcum-doped composite separator with superior wettability and heatproof properties for high-rate lithium metal batteries

Separator is supposed to own outstanding thermal stability,superior wettability and electrolyte uptake,which is essential for developing high-rate and safe lithium metal batteries(LMBs).However,commercial polyolefin separators possess poor wettability and limited electrolyte uptake.For addressing this issue,we put forward a composite separator to implement above functions by doping layered-silicate(talcum)into polyvinylidene fluoride(PVDF).With significant improvement of electrolyte absorption benefiting from the strong adsorption energy values(-1.64-1.70 eV)between talcum and the electrolyte in lithium metal batteries,PVDF/Talcum(PVDF/TM)composite separator owns a small contact angle and superior electrolyte uptake.PVDF/TM composite separator with 10 wt%talcum(T-10)owns a tiny contact angle of 8°,while those of polypropylene(PP)and PVDF are 48°and 20°with commercial electrolyte.Moreover,the addition of thermotolerant talcum endows the T-10 composite separator with great thermostability,whose thermal shrinkage is only 5.39%at 150°C for 0.5 h.The cell with LiFeO4cathode and the T-10 composite separator reaches 91.7 m Ah/g in discharge capacity at 4.8 m A/cm^(2)(10 C),far superior to that with pure PVDF separator(56.3 m Ah/g)and PP(51.4 m Ah/g).

Unified throughout-pore microstructure enables ultrahigh separator porosity for robust high-flux lithium batteries

With small thickness,commercial polyolefin separators own low porosity to ensure sufficient thermomechanical properties,resulting in tortuous and enlarged Li+diffusion pathways that induce large overpotentials and detrimental dendrite growth.As a dilemma,the exploration of highly porous separators has been challenged by their large thickness,impairing the applicability of such pursuits.Herein,an ultraporous architecture is designed to shorten Li+transfer pathways by impregnating electrolyteaffinitive poly(vinylidene fluoride-co-hexafluoropropylene)into ultralight~3μm 3D-polytetrafluoroethylene scaffold(abbreviated as UP3D).The UP3D separator with a porosity of 74%gives rise to 70%enhancement in Li+transference and 77%reduction in Li+transfer resistance(2.67 mΩmm^(−1))and thus enables an ultrahigh Li+flux of 22.7 mA cm^(−2),effectively alleviating Li+concentration gradient across the separator.With the separator,the LiFePO4 half cell delivers a capacity of 118 mAh g^(−1) with an unparalleled capacity retention of 90%after 1000 cycles at 2 C,and a graphite||LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)pouch full cell delivers an areal energy density of 6.8 mWh cm^(−2)at 8.848 mA(1.4 mA cm^(−2))with a high cathode loading of 134.9 mg.Such results,together with the scalable production of the separator,reflect its promising potential in high-flux battery applications of separators that require both ultrahigh porosity and reliability.