Molecular Reactivity and Interface Stability Modification in In-Situ Gel Electrolyte for High Performance Quasi-Solid-State Lithium Metal Batteries

Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply.Despite intensive efforts on electrolytes,uncontrolled interfacial reactions on lithium with electrolyte and patchy interfacial contacts still hinder its practical process.Herein,we bring in rationally designed F contained groups into polymer skeleton via in-situ gelation for the first time to establish quasi-solid-state battery.This method achieves a capacity retention of 90%after 1000 cycles at 0.5C with LiFePO_(4)cathodes.The interface constructed by polymer skeleton and reaction with–CF_(3)lead to the predicted solid electrolyte interface species with high stability.Furthermore,we optimize molecular reactivity and interface stability with regulating F contained end groups in the polymer.Comparisons on different structures reveal that high performance solid stable lithium metal batteries rely on chemical modification as well as stable polymer skeleton,which is more critical to construct robust and steady SEI with uniform lithium deposition.New approach with functional groups regulation proposes a more stable cycling process with a capacity retention of 94.2%at 0.5C and 87.6%at 1C after 1000 cycles with LiFePO_(4) cathodes,providing new insights for the practical development of quasi-solid-state lithium metal battery.

Interface Stability of the SiC Particles/Fe Matrix Composite System

The interface reaction between the SiC particles （ SiCp ） and Fe was stndicd during sintering the SiCp reinforced Fe matrix composites at 1423 K for 1 h. In the composite having 3wt% （weight ratio） SiCp （the 3SiCp/ Fe composite）, the interface reaction products of Fe3 Si, the carbon precipitates, and Fe3 C or pearlite were generated. Fe3 Si coustructs the bright matrix of the reaction zone in the original situation of the SiCp. The carbon precipitates are randondy embedded in the reaction zone. Fe3 C or pearlite exists at the grain boundaries of the Fe matrix. As increasing the SiCp concentration in the SiCp/ Fe composite, the inteusity of the interface reaction between SiCp and Fe iacreases. After the 10SiCp/ Fe composite （ having 10wt .% SiCp ） sintered at 1423 K for 1 h, all of SiCp are decomposed, and replaced by the reaction zone composed of Fe3 Si and the carbon precipitates. No Fe3 C or pearlite was genertaed during the reaction. The effects of the techniques of oxidizing of SiCp , coating SiCp by interaction with the Cr powder, and alloying the Fe matrix by adding the Cr element on the interface stability of the SiCp/ Fe composite system were also investigated, respectitely. The oxide membrane and the coating layer on SiCp can inhibit the interface reaction between SiCp and Fe by isolating SiCp from the Fe matrix during sintering. The interface reaction does not occur in the 3 SiCp/ Fe- 10 Cr composite but in the 3 SiCp/ Fe-5 Cr composite. In the SiCp/ Fe-Cr alloy composites, the interface reaction between SiCp and the Fe- Cr alloys is weaker than that between SiCp and Fe . The Cr element behaves as a diluent, it causes a redaction in the interface reaction, which is proportional to the amount of the element added.

Prediction of Solid-Liquid Interface Stability by Coupling M-S Model with CALPHAD Method

A method to predict the solid-liquid interface stability during unidirectional solidification is developed by coupling M-S model with CALPHAD method. The method was applied to AI-0.38 Zn and AI-0.34 Si-0.14 Mg (wt pct) alloys, and the predicted results were compared with some former experimental data of the two alloys. The good agreement between the calculation results and the experimental data demonstrates the superiority of the present method to the classical one based on constant parameter assumptions.

In situ surface engineering enables high interface stability and rapid reaction kinetics for Ni-rich cathodes

Layered oxide cathodes with high Ni content promise high energy density and competitive cost for Li-ion batteries(LIBs).However,Ni-rich cathodes suffer from irreversible interface reconstruction and undesirable cracking with severe performance degradation upon long-term operation,especially at elevated temperatures.Herein,we demonstrate in situ surface engineering of Ni-rich cathodes to construct a dual ion/electron-conductive NiTiO 3 coating layer and Ti gradient doping(NC90–Ti@NTO)in parallel.The dual-modification synergy helps to build a thin,robust cathode–electrolyte interface with rapid Li-ion transport and enhanced reaction kinetics,and effec-tively prevents unfavorable crystalline phase transformation during long-term cycling under harsh environments.The optimized NC90–Ti@NTO delivers a high reversible capacity of 221.0 mAh g^(-1) at 0.1C and 158.9 mAh g^(-1) at 10C.Impressively,it exhibits a capacity retention of 88.4%at 25?C after 500 cycles and 90.7%at 55?C after 300 cycles in a pouch-type full battery.This finding provides viable clues for stabilizing the lattice and interfacial chemistry of Ni-rich cathodes to achieve durable LIBs with high energy density.

Numerical simulation of cementing displacement interface stability of extended reach wells

The well cementing is important during the extended reach well drilling and the completion, whereas the displacement efficiency and the interface stability are important to guarantee the success of the cementing. In this paper, the interface stability of the cement slurry is simulated using the computational fluid dynamics software. The calculation results indicate that during the displacement, the length of the displacement interface increases with the increase of the deviation angle. The larger the eccentricity, the more significant the velocity difference, along with a longer displacement interface length, a less stable interface, and a lower displacement efficiency. Therefore, to guarantee the cementing quality and maintain a high displacement efficiency, the eccentricity should be controlled within 0.5. Application of a casing centralizer will dramatically improve the interface stability, decrease the dilution zone length of the interface and thus, is beneficial to the slurry cementing and displacement. The simulations are verified with an average absolute deviation less than 3.76% and the 45？ helix angle of the rigid centralizer is recommended. Combining the data of an extended reach well on-site, methods are proposed for improving the displacement efficiency and the interface stability during the well cementing and displacement with complex boreholes. These numerical methods can be used to provide some theoretical guidance for designing the cementing of an extended reach well.

The effect of two-dimensional shear flow on the stability of a crystal interface in a supercooled melt

A model is developed based on the time-related thermal diffusion equations to investigate the effects of twodimensional shear flow on the stability of a crystal interface in the supercooled melt of a pure substance. Similar to the three-dimensional shear flow as described in our previous paper, the two-dimensional shear flow can also be found to reduce the growth rate of perturbation amplitude. However, compared with the case of the Laplace equation for a steady-state thermal diffusion field, due to the existence of time partial derivatives of the temperature fields in the diffusion equation the absolute value of the gradients of the temperature fields increases, therefore destabilizing the interface. The circular interface is more unstable than in the case of Laplace equation without time partial derivatives. The critical stability radius of the crystal interface increases with shearing rate increasing. The stability effect of shear flow decreases remarkably with the increase of melt undercooling.

RESEARCH ON STABILITY OF INTERFACE OF JET CONTAINING SUSPENDED SOLID PARTICLES

The stability equation of interface of two-phase jet and the corresponding particle-gas disturbance velocity ratio equation are derived by means of the phase-coupled model. The stability nares of interface of two-phase jet for different particle properties and the corresponding particle-gas disturbance velocity ratio curves are given out through numerical computation. Further, several important conclusions on effect of particle property on growth and propagation of disturbance of interface of two-phase jet and particle disturbance property me presented on the basis of analyses of the obtained stability curves and particle-gas disturbance velocity ratio curves. These important conclusions can play a guiding role in studying development of two-phase jet and executing artificial controls over it in project practice.

Stability analysis of the moving interface in piston- and non-piston-like displacements

From the macroscopic point of view, expressions involving reservoir and operational parameters are established for investigating the stability of moving interface in piston- and non-piston-like displacements. In the case of axisymmetrical piston-like displacement, the stability is related to the moving interface position and water to oil mobility ratio. The capillary effect on the stability of moving interface depends on whether or not the moving interface is already stable and correlates with the wettability of the reservoir rock. In the case of non-piston-like displacement, the stability of the front is governed by both the relative permeability and the mobility ratio.

A First-principles Study on the Adhesion Strength,Interfacial Stability,and Electronic Properties of Mg/Mg_(2)Y Interface

The interfacial microstructures and configurations directly affect the comprehensive properties of the composites,but their interfacial adhesion mechanism is complicated to expound by experimental methods.In this work,based on the stacking sequence of the Mg/Mg_(2)Y interface models,nine different Mg/Mg_(2)Y interface configurations with top site,bridge site,and hollow site(HCP)under Mg1,Mg_(2),and Y terminations were successfully constructed and systematically explored by first-principles calculations.The results showed that the Mg_(2)Y(0001)surface with Y termination is the most stable when the yttrium chemical potential()is less than-1.09 eV;otherwise,Mg_(2)Y(0001)surface with Mg1 termination is the most stable.The seven-layer Mg(0001)and eleven-layer Mg_(2)Y(0001)slabs are employed to reflect the bulk-like interior properties.Additionally,the Mg(0001)/Mg_(2)Y(0001)with the Y-HCP stacking has the largest interface thermodynamic stability with the value of 2.383 J/m^(2) in all interface configurations owing to its largest work of adhesion.In addition,the interfacial energy of Y-HCP stacking is significantly smaller than those of Mg1-HCP when is approximately less than-0.55 eV,showing that it is more stable.The thermodynamic stability of Mg/Mg_(2)Y with Y-HCP is due to Mg-Y chemical bonds formed between Mg and Y atoms.Lastly,the Mg/Mg_(2)Y interfaces are strong interfaces based on the Griffith fracture theory.

Atom substitution of the solid-state electrolyte Li_(10)GeP_(2)S_(12)for stabilized all-solid-state lithium metal batteries

Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical application.Among all solutions,Ge atom substitution of the solid-state electrolyte LGPS stands out as the most promising solution to this interface problem.A systematic screening framework for Ge atom substitution including ionic conductivity,thermodynamic stability,electronic and mechanical properties is utilized to solve it.For fast screening,an enhanced model Dop Net FC using chemical formulas for the dataset is adopted to predict ionic conductivity.Finally,Li_(10)SrP_(2)S_(12)(LSrPS)is screened out,which has high lithium ion conductivity(12.58 mS cm^(-1)).In addition,an enhanced migration of lithium ion across the LSr PS/Li interface is found.Meanwhile,compared to the LGPS/Li interface,LSrPS/Li interface exhibits a larger Schottky barrier(0.134 eV),smaller electron transfer region(3.103?),and enhanced ability to block additional electrons,all of which contribute to the stabilized interface.The applied theoretical atom substitution screening framework with the aid of machine learning can be extended to rapid determination of modified specific material schemes.

Linear stability analysis on a spherical particle growing from a binary melt under the far-field flow

The solutions of temperature and solute fields around a spherical crystal growing from a binary melt under the far-field flow are obtained.Based on the results,a linear stability analysis on the spherical interface growing from the binary melt under the far-field flow is performed.It is found that the constitutional supercooling effect ahead of the spherical crystal interface under the far-field flow is enhanced compared with that without the flow.The growth rate of the perturbation amplitude at the up-wind side of the spherical crystal interface is larger than that at the down-wind side.The critical stability radius of the crystal interface decreases with the increasing far-field flow velocity.Under the far-field flow,the whole spherical interface becomes more unstable compared with that without the flow.

Recent advances in solid-state metal-air batteries

Solid-state metal-air batteries have emerged as a research hotspot due to their high energy density and high safety.Moreover,side reactions caused by infiltrated gases(O_(2),H_(2)O,or CO_(2))and safety issues caused by liquid electrolyte leakage will be eliminated radically.However,the solid-state metal–air battery is still in its infancy,and many thorny problems still need to be solved,such as the large resistance of the metal/electrolyte interface and catalyst design.This review will summarize some important progress and key issues for solid-state metal-air batteries,especially the lithium-,sodium-,and zinc-based metal-air batteries,clarify some core issues,and forecast the future direction of the solid-state metal-air batteries.

High-performance PVDF-HFP based gel polymer electrolyte with a safe solvent in Li metal polymer battery

Poly(vinylidenefluoride-co-hexafluoropropylene)(PVDF-HFP)based gel polymer electrolytes are widely studied owing to their electrochemical stability and high dielectric constant.However,most gel polymer electrolytes show unsatisfied safety and interface compatibility due to excessive absorption of volatile and flammable liquid solvents.Herein,by using a safe solvent(N-methyl-2-pyrrolidone)with higher boiling(203℃)and flash points(95℃),we initiatively fabricate a flexible PVDF-HFP based gel polymer electrolyte.The obtained gel polymer electrolyte demonstrates a high ionic conductivity of 7.24×10^−4 S cm−1,an electrochemical window of 5.2 V,and a high lithium transference number of 0.57.As a result,the synthesized polymer electrolyte exhibits a capacity retention of 70%after 500 cycles at 0.5 C,and a discharge capacity of 86 mAh g−1 even at a high current rate of 10 C for LiFePO4 based Li metal batteries.Moreover,a stable Li plating/stripping for more than 500 h is achieved under 0.1 mAh at both room temperature and 70℃.Our results indicate that the PVDF-HFP polymer electrolyte is promising for manufacturing safe and high-performance Li metal polymer batteries.

Insights Into the Interfacial Degradation of High-Voltage All-Solid-State Lithium Batteries

Poly(ethylene oxide)(PEO)-based solid polymer electrolyte(SPE)is considered as a promising solid-state electrolyte for all-solid-state lithium batteries(ASSLBs).Nevertheless,the poor interfacial stability with high-voltage cathode materials(e.g.,LiCoO_(2))restricts its application in high energy density solid-state batteries.Herein,high-voltage stable Li_(3)AlF_(6) protective layer is coated on the surface of LiCoO_(2) particle to improve the performance and investigate the failure mechanism of PEO-based ASSLBs.The phase transition unveils that chemical redox reaction occurs between the highly reactive LiCoO_(2) surface and PEO-based SPE,resulting in structure collapse of LiCoO_(2),hence the poor cycle performance of PEO-based ASSLBs with LiCoO_(2) at charging voltage of 4.2 V vs Li/Li+.By sharp contrast,no obvious structure change can be found at the surface of Li_(3)AlF_(6)-coated LiCoO_(2),and the original layered phase was well retained.When the charging voltage reaches up to 4.5 V vs Li/Li+,the intensive electrochemical decomposition of PEO-based SPE occurs,leading to the constant increase of cell impedance and directly causing the poor performance.This work not only provides important supplement to the failure mechanism of PEO-based batter-ies with LiCoO_(2),but also presents a universal strategy to retain structure stability of cathode-electrolyte interface in high-voltage ASSLBs.

Approaching High-Performance Lithium Storage Materials by Constructing Hierarchical CoNiO_(2)@CeO_(2)Nanosheets

In this work,the hierarchical CoNiO_(2)@CeO_(2)nanosheet composites were successfully prepared by a one-step hydrothermal process with a subsequent annealing process for the first time.The CeO_(2)nanoparticles successfully deposit on the surface of CoNiO_(2)nanosheet,and benefit the improvement of electrical contact between CoNiO_(2)and CeO_(2).CeO_(2)modification improve the reversibility of insertion/extraction of Li-ions and electrochemical reaction activity,and promotes the transport of Li-ions.Benefited of the unique architecture and component,the CoNiO_(2)@CeO_(2)nanosheet composites show high-reversible capacities,excellent cycling stability and good rate capability.The CoNiO_(2)@CeO_(2)(5.0 wt%)shows a charge/discharge capacity of 867.1/843.2 m Ah g^(-1)after 600 cycles at 1 A g^(-1),but the pristine CoNiO_(2)@CeO_(2)nanosheet only delivers a charge/discharge capacity of 516.9/517.6 m Ah g^(-1)after 500 cycles.The first-principles calculation reveals that valid interfaces between CeO_(2)and NiCoO_(2)can be formed,and the formation process of the interfaces is exothermic.The strong interfacial interaction resulting in an excellent structure stability and thus a cycling stability of the CoNiO_(2)@CeO_(2)material.This work provides an effective strategy to develop highperformance anode materials for advanced a lithium-ion battery,and the CoNiO_(2)@CeO_(2)nanosheet shows a sizeable potential as an anode material for next generation of high-energy Li-ion batteries.

Progress on direct assembly approach for in situ fabrication of electrodes of reversible solid oxide cells

Reversible solid oxide cells(SOCs)are very efficient and clean for storage and regeneration of renewable electrical energy by switching between electrolysis and fuel cell modes.One of the most critical factors governing the efficiency and durability of SOCs technology is the stability of the interface between oxygen electrode and electrolyte,which is conventionally formed by sintering at a high temperature of~1000–1250℃,and which suffers from delamination problem,particularly for reversibly operated SOCs.On the other hand,our recent studies have shown that the electrode/electrolyte interface can be in situ formed by a direct assembly approach under the electrochemical polarization conditions at 800℃and lower.The direct assembly approach provides opportunities for significantly simplifying the cell fabrication procedures without the doped ceria barrier layer,enabling the utilization of a variety of high-performance oxygen electrode materials on barrier layer–free yttria-stabilized zirconia(YSZ)electrolyte.Most importantly,the in situ polarization induced interface shows a promising potential as highly active and durable interface for reversible SOCs.The objective of this progress report is to take an overview of the origin and research progress of in situ fabrication of oxygen electrodes based on the direct assembly approach.The prospect of direct assembly approach in the development of effective SOCs and in the fundamental studies of electrode/electrolyte interface reactions is discussed.

A Pragmatic Method to Determine Transient Stability Constrained with Interface Real Power Flow Limits via Power System Scenario Similarity

In practical power systems,operators generally keep interface flowing under the transient stability constrained with interface real power flow limits(TS-IRPFL)to guarantee transient stability of the system.Many methods of computing TS-IRPFL have been proposed.However,in practice,the method widely used to determine TS-IRPFL is based on selection and analysis of typical scenarios as well as scenario matching.First,typical scenarios are selected and analyzed to obtain accurate limits,then the scenario to be analyzed is matched with a certain typical scenario,whose limit is adopted as the forecast limit.In this paper,following the steps described above,a pragmatic method to determine TS-IRPFL is proposed.The proposed method utilizes data-driven tools to improve the steps of scenario selection and matching.First of all,we formulate a clear model of power system scenario similarity.Based on the similarity model,we develop a typical scenario selector by clustering and a scenario matcher by nearest neighbor algorithm.The proposed method is pragmatic because it does not change the existing procedure.Moreover,it is much more reasonable than the traditional method.Test results verify the validity of the method.

Solid-state lithium-ion batteries for grid energy storage:opportunities and challenges

The energy crisis and environmental pollution drive more attention to the development and utilization of renewable energy.Considering the capricious nature of renewable energy resource,it has difficulty supplying electricity directly to consumers stably and efficiently,which calls for energy storage systems to collect energy and release electricity at peak periods.Due to their flexible power and energy,quick response,and high energy conversion efficiency,lithium-ion batteries stand out among multiple energy storage technologies and are rapidly deployed in the grid.Pursuing superior performance and ensuring the safety of energy storage systems,intrinsically safe solid-state electrolytes are expected as an ideal alternative to liquid electrolytes.In this review,we systematically evaluate the priorities and issues of traditional lithium-ion batteries in grid energy storage.Beyond lithium-ion batteries containing liquid electrolytes,solid-state lithium-ion batteries have the potential to play a more significant role in grid energy storage.The challenges of developing solid-state lithium-ion batteries,such as low ionic conductivity of the electrolyte,unstable electrode/electrolyte interface,and complicated fabrication process,are discussed in detail.Additionally,the safety of solid-state lithium-ion batteries is re-examined.Following the obtained insights,inspiring prospects for solid-state lithium-ion batteries in grid energy storage are depicted.

Trimethyl phosphate-enhanced polyvinyl carbonate polymer electrolyte with improved interfacial stability for solid-state lithium battery

The polyvinyl carbonate(PVC)polymer solid electrolyte can be in-situ generated in the assembled lithium-ion battery(LIBs);however,its rigid characteristic leads to uneven interface contact between electrolyte and electrodes.In this work,trimethyl phosphate(TMP)is introduced into the precursor solution for in-situ generation of flexible PVC solid electrolyte to improve the interfacial contact of elec-trolyte and electrodes together with ionic conductivity.The PVC-TMP electrolyte exhibits good interface compatibility with the lithium metal anode,and the lithium symmetric battery based on PVC-TMP electrolyte shows no obvious polarization within 1000 h cycle.As a consequence,the initial interfacial resistance of battery greatly decreases from 278Ω(LiFePO_(4)(LFP)/PVC/Li)to 93Ω(LFP/PVC-TMP/Li)at 50℃,leading to an improved cycling stability of the LFP/PVC-TMP/Li battery.Such in-situ preparation of solid electrolyte within the battery is demonstrated to be very significant for commercial application.

Air exposure towards stable Li/Li_(10)GeP_(2)S_(12) interface for all-solid-state lithium batteries

Moist air is a great challenge for manufacturing sulfide-based all-solid-state lithium batteries as the water in air will lead to severe decomposition of sulfide electrolytes and release H2S gas.However,different with direct reaction with water,short-period air exposure of Li_(10)GeP_(2)S_(12) sulfide electrolyte with controlled humidity can greatly enhance the stability of Li_(10)GeP_(2)S_(12) against lithium metal,thus realizing stable Li_(10)GeP_(2)S_(12) based all-solid-state lithium metal batteries.During air exposure,partial hydrolysis reaction occurs on the surface of Li_(10)GeP_(2)S_(12) pellets,rapidly generating a protective decomposition layer of Li4P2S6,GeS2 and Li2HPO3 in dozens of seconds.This ionically conductive but electronically insulation protecting layer can effectively prevent the severe interface reaction between Li_(10)GeP_(2)S_(12) and lithium metal during electrochemical cycling.The Li/40s-air-exposed Li_(10)GeP_(2)S_(12)/Li cell shows long cycling stability for 1000 h.And the LiCoO_(2)/40s-air-exposed Li_(10)GeP_(2)S_(12)/Li batteries present good rate capability and long cyclic performances,showing capacity retention of 80%after 100 cycles.