Alkali metal batteries based on lithium, sodium, and potassium anodes and sulfur-based cathodes are regarded as key for next-generation energy storage due to their high theoretical energy and potential cost effectiveness. However, metal-sulfur batteries remain challenged by several factors, including polysulfides' (PSs) dissolution, sluggish sulfur redox kinetics at the cathode, and metallic dendrite growth at the anode. Functional separators and interlayers are an innovative approach to remedying these drawbacks. Here we critically review the state-of-the-art in separators/interlayers for cathode and anode protection, covering the Li-S and the emerging Na-S and K-S systems. The approaches for improving electrochemical performance may be categorized as one or a combination of the following: Immobilization of polysulfides (cathode); catalyzing sulfur redox kinetics (cathode); introduction of protective layers to serve as an artificial solid electrolyte interphase (SEI) (anode); and combined improvement in electrolyte wetting and homogenization of ion flux (anode and cathode). It is demonstrated that while the advances in Li-S are relatively mature, less progress has been made with Na-S and K-S due to the more challenging redox chemistry at the cathode and increased electrochemical instability at the anode. Throughout these sections there is a complementary discussion of functional separators for emerging alkali metal systems based on metal-selenium and the metal-selenium sulfide. The focus then shifts to interlayers and artificial SEI/cathode electrolyte interphase (CEI) layers employed to stabilize solid-state electrolytes (SSEs) in metal-sulfur solid-state batteries (SSBs). The discussion of SSEs focuses on inorganic electrolytes based on Li- and Na-based oxides and sulfides but also touches on some hybrid systems with an inorganic matrix and a minority polymer phase. The review then moves to practical considerations for functional separators, including scaleup issues and Li-S technoeconomics. The review concludes with an outlook section, where we discuss emerging mechanics, spectroscopy, and advanced electron microscopy (e.g. cryo-transmission electron microscopy (cryo-TEM) and cryo-focused ion beam (cryo-FIB))-based approaches for analysis of functional separator structure-battery electrochemical performance interrelations. Throughout the review we identify the outstanding open scientific and technological questions while providing recommendations for future research topics.

Review of Multifunctional Separators: Stabilizing the Cathode and the Anode for Alkali (Li, Na, and K) Metal-Sulfur and Selenium Batteries.

Experimental parametric studies on the performance and mixing characteristics of a low area ratio rectangular supersonic gaseous ejector by varying the secondary flow rate

Thanks to their high energy density, lithium/sodium metal batteries (LMBs/SMBs) are considered to be the most promising next-generation energy storage system. However, the instability of the electrode/electrolyte interface and dendrite growth seriously hinders commercial application of LMBs/SMBs. In addition, traditional liquid electrolytes are inflammable and explosive. As a key part of the battery, the electrolyte plays an important role in solving the abovementioned problems. Although solid electrolytes can alleviate dendrite growth and liquid electrolyte leakage, their low ionic conductivity and poor interfacial contact are not conducive to improvement of overall LMBs/SMB performances. Therefore, it is necessary to find a balance between liquid and solid electrolytes. Gel polymer electrolytes (GPEs) are one means for achieving high-performance LMBs/SMBs because they combine the advantages of liquid and solid electrolytes. Metal-organic frameworks (MOFs) benefit from high specific surface areas, ordered internal porous structures, organic-inorganic hybrid properties, and show great potential in modified electrolytes. Here, Cu-based MOF-supported poly(ethylene oxide) composite gel polymer electrolytes (CGPEs) were prepared by ultraviolet curing. This CGPE exhibited high ionic conductivity, a wide electrochemical window, and a high ion transference number. In addition, it also exhibited excellent cycle stability in symmetric batteries and LMBs/SMBs. This study showed that CGPE had great practical application potential in the next-generation LMBs/SMBs.

Metal-Organic Framework-Supported Poly(ethylene oxide) Composite Gel Polymer Electrolytes for High-Performance Lithium/Sodium Metal Batteries.

This paper aims to investigate the secondary flow characteristics and the associated vacuum generation caused with increase in the primary pressure ramping in zero-secondary flow ejectors. The sudden expansion of the primary jet into the diffuser during the ejector start-up results in flow separation from the shear layer formed between the primary and inducted flows and produces large recirculation bubbles in the top and bottom sides of the jet. These recirculation bubbles cause an induced flow from ambient air into the diffuser duct as well. The fluid supply from the reverse flow due to the shear layer separation and the induced flow from ambient air provide a counter momentum against fluid entrainment from a vacuum chamber. As a result of this, the initial vacuum generation process progresses in a slow rate. Thereafter, the primary jet expansion reaches a critical level and a rapid vacuum generation can be seen. It is found that with the jet expansion reaching a critical level, the fluid supply from the reverse flow is suddenly entrained back into the main jet at the maximum jet expansion point. This suddenly reduces the counter-momentum which has been prohibiting the entrainment of fluid from the vacuum chamber and results in rapid evacuation. This is followed by a stage in which the vacuum chamber pressure is increasing due to the attainment of a constant Mach number at the diffuser inlet and the jet pressure ramping. It is found that the secondary flow dynamics and the vacuum generation processes in rectangular and round ejectors show a close resemblance.

Physics of vacuum generation in zero-secondary flow ejectors

The impinging shock of varying strengths on the free shear layer in a confined supersonic cavity flow is studied numerically using the detached-eddy simulation. The resulting spatiotemporal variations are analyzed between the different cases using unsteady statistics, $x-t$ diagrams, spectral analysis, and modal decomposition. A cavity of length to depth ratio $[L/D]=2$ at a freestream Mach number of $M_\infty = 1.71$ is considered to be in a confined passage. Impinging shock strength is controlled by changing the ramp angle ($\theta$) on the top-wall. The static pressure ratio across the impinging shock ($p_2/p_1$) is used to quantify the impinging shock strength. Five different impinging shock strengths are studied by changing the pressure ratio: $1.0,1.2,1.5,1.7$ and $2.0$. As the pressure ratio increases from 1.0 to 2.0, the cavity wall experiences a maximum pressure of 25% due to shock loading. At [$p_2/p_1]=1.5$, fundamental fluidic mode or Rossiter's frequency corresponding to $n=1$ mode vanishes whereas frequencies correspond to higher modes ($n=2$ and $4$) resonate. Wavefronts interaction from the longitudinal reflections inside the cavity with the transverse disturbances from the shock-shear layer interactions is identified to drive the strong resonant behavior. Due to Mach-reflections inside the confined passage at $[p_2/p_1]=2.0$, shock-cavity resonance is lost. Based on the present findings, an idea to use a shock-laden confined cavity flow in an enclosed supersonic wall-jet configuration as passive flow control or a fluidic device is also demonstrated.

Shock and shear layer interaction in a confined supersonic cavity flow

Design of porous calcium phosphate based gel polymer electrolyte for Quasi-solid state sodium ion battery

This study investigates the shock transformation in an underexpanded jet in a confined duct when the jet total pressure is increased. Experimental study reveals that the Mach reflection (MR) in the fully underexpanded jet transforms to a regular reflection (RR) at a certain jet total pressure. It is observed that neither the incident shock angle nor the upstream Mach number varies during the MR–RR shock transformation. This is in contradiction to the classical MR–RR transformations in internal flow over wedges and in underexpanded open jets. This transformation is found to be a total pressure variation induced transformation, which is a new kind of shock transformation. The present study also reveals that the critical jet total pressures for MR–RR and RR–MR transformations are not the same when the primary pressure is increasing and decreasing, suggesting a hysteresis in the shock transformations.

Shock transformation and hysteresis in underexpanded confined jets

An experimental study has been carried out to investigate the nature of transients in vacuum ejector flows during start-up and the dynamics in flow characteristics. The results show that the secondary stream induction progresses with non-uniform rates with the ramping primary jet pressure during start-up. The initial evacuation period is subjected to gradual and highly perturbed secondary fluid entrainment. In this phase, the secondary stream induction by the shear layer is asymmetric leading to an un-even vacuum generation in the secondary chamber. In the second phase, the secondary pressure fluctuations are found to be ceased for a critical primary jet pressure followed by a rapid induction of the secondary fluid till the primary jet expands to the diffuser wall. The transition from the first phase to the second phase is caused by the secondary stream flow choking in the diffuser. Following the second phase, a stable stage exists in the third phase in which the vacuum pressure decreases only marginally. Any further attempt to increase the secondary chamber vacuum level beyond the third phase, by increasing the primary jet total pressure, results in flow reversal into the secondary chamber, spoiling the already achieved vacuum level. In the fourth phase of start-up, a complicated shock interaction transformation from a Mach reflection (MR) to regular reflection (RR) occurs within the diffuser. It is also observed that the primary jet pressures for the minimum secondary chamber pressure, the minimum secondary pressure, and the primary pressure for MR-RR transformation decrease initially with increase in diffuser length and then increase. It is found that the decreasing and increasing trends are caused by the pressure recovery and Fanno effects, respectively.

Flow transients in un-started and started modes of vacuum ejector operation

In recent times, shock tube flows have been widely employed in many micro-scale devices in the fields of propulsion technology, micro-heat engines, particle delivery systems, and so on. The very small length scales in such micro-shock tubes make the flow physics more complicated compared to the ordinary macro-shock tubes. The major differences in the flow features are the profound influences of wall effects and rarefaction effects. The rarefaction effect alters the boundary layer structure by imparting additional velocity and thermal gradients to the wall-bounded fluid. These phenomena can strongly affect the micro-shock tube flow characteristics such as shock–contact wave speeds, wave propagations, hot and cold zone properties. The main objective of the present work is to produce a detailed understanding on the wave propagation characteristics in a micro-shock tube under rarefied conditions using computational fluid dynamics methods. The shock–contact interface movement under different operating conditio...

R. Arun Kumar

Papers

Physics of vacuum generation in zero-secondary flow ejectors

Design of porous calcium phosphate based gel polymer electrolyte for Quasi-solid state sodium ion battery

Shock transformation and hysteresis in underexpanded confined jets

Flow transients in un-started and started modes of vacuum ejector operation

Computational analysis of the wave motions in micro-shock tube flow