Theoretical Energy Density Research Articles

Combustion and energy performance of multiple aluminum-based alloy particles

The long ignition delay time, high ignition temperature and agglomeration prevent the aluminum (Al) particles from fully releasing the chemical energy stored within them during combustion. Al-based alloy fuels with high energy density and excellent combustion performance have become a potential candidate for replacement with pure Al. Therefore, understanding the combustion and energy performance of Al-based alloys is beneficial for the development of Al-based energetic materials. Herein, the combustion and energy performance of pure Al and three Al-based alloys were comparatively investigated by means of a thermal analysis system, an ignition and combustion test apparatus, and a variety of physicochemical property characterizations. The results showed that all three Al-based alloys contained at least one intermetallic compound. Al-boron (B) and Al-magnesium (Mg)-B alloys had higher theoretical energy densities than pure Al, while Al-Mg did not. The thermal oxidation properties of all three alloys were significantly better than those of pure Al. Compared with pure Al, the three alloys showed higher burning rate, shorter ignition delays, more vigorous combustion, and higher burnout at room pressure in air. This is still true after adding AP. According to the compositions of the condensed combustion products, the possible chemical reactions during the combustion of the alloys were speculated. Grasping the combustion mechanisms of the alloys is challenging due to the relative lack of thermodynamic data on intermetallic compounds. Finally, a comprehensive comparison of the combustion processes of pure Al and alloys was made. Although the Al-Mg alloy does not have the same theoretical energy density as pure Al, the more outstanding combustion performance and fewer two-phase flow losses may make up for the gap in theoretical energy density.

Addition of a Polar, Porous Phase-Inversion-PVDF Membrane to Lithium–Sulfur Cells (LSBs) Already with a Microporous Polypropylene Separator Enhances the Battery Performance

Lithium–sulfur batteries (LSBs) are widely studied as an alternative to lithium-ion batteries, this emphasis being due to their high theoretical energy density and low cost, and to the high natural abundance of sulfur. Lithium polysulfide shuttling and lithium dendrite growth have limited their commercialization. Porous polyvinylidene fluoride (PVDF) separators have shown improved performance (relative to hydrocarbon separators) in lithium-ion batteries due to faster lithium-ion migration and higher Li+ transference number. A thin polar PVDF membrane has now been fabricated via phase inversion (an immersion-precipitation method) yielding a β (polar) phase concentration of 72%. Preparation from commercial PVDF used dimethylformamide (DMF) solvent at the optimized crystallizing temperature of 70 °C, and pores in the membrane were generated by exchange of DMF with deionized water as non-solvent. The polar PVDF film produced has the advantages of being ultrathin (15 µm), lightweight (1.15 mg cm−2), of high porosity (75%) and high wettability (84%), and it shows enhanced thermal stability relative to polypropylene (PP). The porous, polar PVDF membrane was combined with a commercially available PP membrane to give a hybrid, two-layer, separator combination for LSBs. A synergy was created in the two-layer separator, providing high sulfur utilization and curbing polysulfide shuttling. The electrochemical performance with the hybrid separator (PP–β-PVDF) was evaluated in LSB cells and showed good cyclability and rate capability: those LSB cells showed a stable capacity of 750 mA h g−1 after 100 cycles at 0.1 C, much higher than that for otherwise-identical cells using a commercial PP-only separator (480 mA h g−1).

Kinetics enhancement of an advanced separator modified by vanadium-based MXene for Li-S batteries

Li-S batteries are promising because of the ultrahigh theoretical energy density (2600 Wh kg−1), however the severe shuttle effect of polysulfides and hysteresis of reaction kinetics hinder the application of Li-S batteries. Hence, this work raises a vanadium-based MXene modified separator for Li-S batteries, which can effectively inhibit the irreversible loss of polysulfides and further accelerate their rapid conversion. In addition, the kinetic enhancement role of this functionalized separator is studied from the electrochemistry perspective. As expected, both the cyclic stability and rate performance of Li-S batteries with this advanced separator are significantly improved, which highlight the application prospect in the field of energy storage and conversion.

Open-cycle thermochemical energy storage for building space heating: Practical system configurations and effective energy density

Salt-hydrate thermochemical materials (TCM) are promising candidates for energy storage systems for building space heating due to their high theoretical energy density and the need for low regeneration temperature. However, water vapor is required to drive the hydration process of the TCM reactor, which poses a challenge during winter when water vapor is typically scarce. Using indoor air directly lowers the building's humidity to an unconformable level in practice, while the cold outdoor air contains limited moisture. Here we consider different integration strategies for open-cycle TCM reactors in buildings and develop a model to simulate their thermal performance across diverse buildings and climates, specifically for building space heating. The potential energy densities and the levelized cost of storage of the TCM reactor are evaluated in practical scenarios to demonstrate the load-shifting potential of TCM systems for heating applications. We use a strontium chloride (SrCl2)-based composite as the baseline and explore the impact of various reactor and material changes to the energy density and levelized cost of storage.

High-Electrochemical-Activity Composite Cathode Enabled by Fast Segmental Relaxation for Solid-State Lithium-Sulfur Batteries.

Solid-state lithium-sulfur batteries (SSLSBs) have attracted a great deal of attention because of their high theoretical energy density and intrinsic safety. However, their practical applications are severely impeded by slow redox kinetics and poor cycling stability. Herein, we revealed the detrimental effect of aggregation of lithium polysulfides (LiPSs) on the redox kinetics and reversibility of SSLSBs. As a paradigm, we introduced a multifunctional hyperbranched ionic conducting (HIC) polymer serving as a solid polymer electrolyte (SPE) and cathode binder for constructing SSLSBs featuring high electrochemical activity and high cycling stability. It is demonstrated that the unique structure of the HIC polymer with numerous flexible ether oxygen dangling chains and fast segmental relaxation enables the dissociation of LiPS clusters, facilitates the conversion kinetics of LiPSs, and improves the battery's performance. A Li|HIC SPE|HIC-S battery, in which the HIC polymer acts as an SPE and cathode binder, exhibits an initial capacity of 910.1 mA h gS-1 at 0.1C and 40 °C, a capacity retention of 73.7% at the end of 200 cycles, and an average Coulombic efficiency of approximately 99.0%, demonstrating high potential for application in SSLSBs. This work provides insights into the electrochemistry performance of SSLSBs and provides a guideline for SPE design for SSLSBs with high specific energy and high safety.

Synergistic Electrocatalysis and Spatial Nanoconfinement to Accelerate Sulfur Conversion Kinetics in Aqueous Zn−S Battery

AbstractAqueous zinc batteries based on the conversion‐type sulfur cathodes are promising in energy storage system due to the high theoretical energy density, low cost, and good safety. However, the multi‐electron solid‐state intermediate conversion reaction of sulfur cathodes generally possess sluggish kinetics, which leads to lower discharge voltage and inefficient sulfur utilization, thus suppressing the practical energy density. Herein, sulfur nanoparticles derived from metal–organic frameworks confined in situ within electrospun fibers derived sulfur and nitrogen co‐doped carbon nanofibers (S@S,N−CNF) composite, which possesses yolk–shell S@C nanostructure, is fabricated through successive sulfidation, pyrolysis, and sulfide oxidation processes, and served as a high‐performance cathode material for Zn−S battery. The S and N dopants on carbon can collectively catalyse sulfur reduction reaction (SRR) by lowering energy barrier and accelerating kinetics to increase discharge voltage and specific capacity. Meanwhile, the yolk–shell S@C structure with spatially confined S nanoparticle yolks is beneficial to improve charge transfer and lower activation energy, thus further expediting SRR kinetics. Furthermore, extensive density functional theory (DFT) calculations reveal that S and N dual‐doping can thermodynamically and dynamically reduce the energy barrier of rate‐determining step (i.e., the transformation of *ZnS4 into *ZnS2) for the overall SRR, thereby significantly accelerating SRR kinetics.

Synergistic Electrocatalysis and Spatial Nanoconfinement to Accelerate Sulfur Conversion Kinetics in Aqueous Zn-S Battery.

Aqueous zinc batteries based on the conversion-type sulfur cathodes are promising in energy storage system due to the high theoretical energy density, low cost, and good safety. However, the multi-electron solid-state intermediate conversion reaction of sulfur cathodes generally possess sluggish kinetics, which leads to lower discharge voltage and inefficient sulfur utilization, thus suppressing the practical energy density. Herein, sulfur nanoparticles derived from metal-organic frameworks confined in situ within electrospun fibers derived sulfur and nitrogen co-doped carbon nanofibers (S@S,N-CNF) composite, which possesses yolk-shell S@C nanostructure, is fabricated through successive sulfidation, pyrolysis, and sulfide oxidation processes, and served as a high-performance cathode material for Zn-S battery. The S and N dopants on carbon can collectively catalyse sulfur reduction reaction (SRR) by lowering energy barrier and accelerating kinetics to increase discharge voltage and specific capacity. Meanwhile, the yolk-shell S@C structure with spatially confined S nanoparticle yolks is beneficial to improve charge transfer and lower activation energy, thus further expediting SRR kinetics. Furthermore, extensive density functional theory (DFT) calculations reveal that S and N dual-doping can thermodynamically and dynamically reduce the energy barrier of rate-determining step (i.e., the transformation of *ZnS4 into *ZnS2) for the overall SRR, thereby significantly accelerating SRR kinetics.

A Conductive Binder Based on Mesoscopic Interpenetration with Polysulfides Capturing Skeleton and Redox Intermediates Network for Lithium Sulfur Batteries

AbstractThe practical application of lithium‐sulfur batteries with high theoretical energy density and readily available cathode active materials is hampered by problems such as sulfur insulation, dramatic volume changes, and polysulfide shuttling. The targeted development of novel binders is the most industrialized solution to the problem of sulfur cathodes. Herein, an aqueous conductive emulsion binder with the sulfonate‐containing hard elastic copolymer core and the conjugate polymer shell, which is capable of forming a bicontinuous mesoscopic interpenetrating polymer network, is synthesized and investigated. Not only can the elastic skeleton formed by the copolymer bind the active substance under drastic volume changes, but also the rich ester and cyanide groups in it can effectively capture lithium polysulfide. Meanwhile, the conducting skeleton consisting of poly(3,4‐ethylenedioxythiophene) both provides the additional charge conduction pathways and acts as the redox intermediates, significantly accelerating the kinetic process of lithium polysulfide conversion. Based on the synergistic effect of the above mechanisms, the use of the prepared binder on the sulfur carbon cathode significantly improves the rate performance and cycle stability of lithium sulfur batteries.

A Conductive Binder Based on Mesoscopic Interpenetration with Polysulfides Capturing Skeleton and Redox Intermediates Network for Lithium Sulfur Batteries.

The practical application of lithium-sulfur batteries with high theoretical energy density and readily available cathode active materials is hampered by problems such as sulfur insulation, dramatic volume changes, and polysulfide shuttling. The targeted development of novel binders is the most industrialized solution to the problem of sulfur cathodes. Herein, an aqueous conductive emulsion binder with the sulfonate-containing hard elastic copolymer core and the conjugate polymer shell, which is capable of forming a bicontinuous mesoscopic interpenetrating polymer network, is synthesized and investigated. Not only can the elastic skeleton formed by the copolymer bind the active substance under drastic volume changes, but also the rich ester and cyanide groups in it can effectively capture lithium polysulfide. Meanwhile, the conducting skeleton consisting of poly(3,4-ethylenedioxythiophene) both provides the additional charge conduction pathways and acts as the redox intermediates, significantly accelerating the kinetic process of lithium polysulfide conversion. Based on the synergistic effect of the above mechanisms, the use of the prepared binder on the sulfur carbon cathode significantly improves the rate performance and cycle stability of lithium sulfur batteries.

Iodine-induced self-depassivation strategy to improve reversible kinetics in Na-Cl2 battery

Rechargeable sodium-chlorine (Na-Cl2) batteries show high theoretical specific energy density and excellent adaptability for extreme environmental applications. However, the reported cycle life is mostly less than 500 cycles, and the understanding of battery failure mechanisms is quite limited. In this work, we demonstrate that the substantially increased voltage polarization plays a critical role in the battery failure. Typically, the passivation on the porous cathode caused by the deposition of insulated sodium chloride (NaCl) is a crucial factor, significantly influencing the three-phase chlorine (NaCl/Na+, Cl-/Cl2) conversion kinetics. Here, a self-depassivation strategy enabled by iodine anion (I-)-tuned NaCl deposition was implemented to enhance the chlorine reversibility. The nucleation and growth of NaCl crystals are well balanced through strong coordination of the NaI deposition-dissolution process, achieving depassivation on the cathode and improving the reoxidation efficiency of solid NaCl. Consequently, the resultant Na-Cl2 battery delivers a super-long cycle life up to 2000 cycles.

High-Energy-Density High-Power-Density Micro Aluminum-Air Batteries for Small Scale Quadcopters

Small-scale quadcopters are increasingly used in various fields, including rescue, surveillance and precision agriculture. The predominant energy storage system for such quadcopters has been the micro lithium-ion battery (mLIB). Two of the most important design metrics for power sources used in quadcopters are specific power and specific energy. The specific energy determines the flight duration of the quadcopters, while specific power is necessary for maneuverability and takeoff. The mLIB can easily meet the power requirement of small scale quadcopters; however, the limited energy density of mLIBs (exacerbated by the packaging overhead of these batteries as scales shrink) constrains their flight duration. To increase the flight time, aluminum-air batteries (AABs), with a theoretical energy density twenty times greater than conventional lithium-ion batteries, are being explored. [1] Despite AAB’s high theoretical energy density, the conventional AAB lacks the high-power performance of LIBs. [2] To fulfill the demanding power requirements of small scale quadcopters, the AAB cell has been re-engineered to enhance power capability while maintaining high energy density.To maximize AAB energy and power density at the cell level, it is imperative to address the issue of battery packages that add weight without contributing to electrochemical performance. A light-weight battery packaging approach is developed for the micro-AAB (mAAB). In the context of AABs, the primary function of the battery package is to retain the aqueous electrolyte within the cell. Typically, the cathode of an AAB is constructed using a carbon cloth, doped with a layer of polytetrafluoroethylene (PTFE). This hydrophobic carbon cloth cathode effectively retains the aqueous electrolyte. In order to increase the mechanical integrity of mAAB pouch cells, 3D printed polypropylene is utilized as the body frame of mAABs, providing a robust and lightweight structure. The carbon cloth cathode is affixed to the 3D printed polypropylene using epoxy, as shown in Figure 1A. An image of an assembled 2-gram mAAB pouch cell is shown in Fig 1B. Remarkably, the electrochemically inactive packaging materials contribute to less than 13% of the total cell weight, achieving the goal of minimizing packaging material to enhance battery performance. As a comparison, the packaging material of gram-scale mLIBs can contribute to over 30% of total cell weight. Furthermore, in contrast to traditional aluminum-air battery designs, the pouch cell architecture optimizes cathode area exposure, which is advantageous for high-power applications.The anode structure is also engineered for high power capability. Figure 2A shows that increasing the anode/cathode area ratio can augment areal power density. Therefore, a multi-layer anode structure, supported by 3D printed polypropylene, is developed for mAAB pouch cells. This design effectively increases the anode/cathode surface area ratio and enables rapid ion and electron transport within the multi-layer anode, optimizing power performance. A schematic of a 3D printed polypropylene supported multi-layer anode structure is shown in Figure 2B.The electrochemical performance of assembled mAAB pouch cells is evaluated to assess their suitability for the demanding requirements of small scale quadcopter applications. Figure 3A provides a comparative analysis of power densities between mAABs and commercial micro-quadcopter mLIBs. Notably, mAABs exhibit a peak power density exceeding 1500 Wh/kgbattery at 4 Amp, surpassing that of mLIBs. Battery weight encompasses anode, cathode, electrolyte and all necessary battery packaging, confirming that mAABs can meet the power demands of micro-quadcopters. In Figure 3B, the energy density of mAABs is compared to commercial mLIBs. When the power density is above 500 W/kgbattery, a threshold sufficient to lift a quadrotor drone, mAABs exhibit an energy density of 320 Wh/kgbattery, which is multiple times higher than that of mLIBs. [3] Notably, the anode utilization of the mAAB exceeds 85%, underscoring the effectiveness of the multi-layer anode design. This superior electrochemical performance emphasizes the superior capability of mAABs, indicating their potential as an advanced power source for long flight duration small scale quadcopters.

Exploring the Role of Redox-Shuttle Mediators in Lithium-Sulfur Batteries

The lithium-ion battery (LIB) is widely acknowledged as the state-of-the-art battery technology today and is used in consumer electronics, stationary storage, and electrified transportation1,2. However, there is a drive towards developing technologies with higher energy densities. The lithium-sulfur battery is one of the most promising next-generation batteries for high-energy applications, due to its high theoretical gravimetric energy density of 2567 W h kg-1, low raw material costs, and reduced environmental impact3. Despite these potential advantages, lithium-sulfur batteries are still beset with difficulties, one of the most significant is the so-called “polysulfide shuttle effect.” Operation of the battery involves the conversion of sulfur to polysulfide species, which dissolve into the electrolyte and diffuse to the lithium metal electrode, leading to loss of active material. This results in poor cycle life, rapid capacity fading and low coulombic efficiencies4.The use of dissolved, electrochemically active redox mediators could mitigate these effects by catalysing sulfur redox reactions during cell cycling. While it is generally agreed that the redox potential of the mediators is a key factor in their operation, no report to date has conclusively demonstrated how mediators of varying potentials can target specific sulfur redox reactions. Herein, we report a study of the mediators 9-fluorenone (9-FO), duroquinone (DQ), 2,6-di-tert-butyl-1,4-benzoquinone (TBBQ) and 1,5-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)anthra-9,10-quinone (AQT) to understand their interactions with sulfur, lithium polysulfides, lithium sulfide and lithium metal5. We use liquid-chromatography mass spectrometry (LC-MS) to isolate various polysulfide chain lengths after reaction with mediators. It is observed that high potential redox mediators, such as TBBQ, are better able to drive Li2S oxidation to higher polysulfide chain lengths, and low potential redox mediators such as 9-FO push sulfur towards lower chain polysulfides. This offers a novel and effective approach to screening suitable redox-active molecules. Galvanostatic cycling is employed to relate these chemical interactions to enhanced cell performance. Developing a fundamental understanding of how redox mediators operate in a cell will aid in the molecular design of novel redox-active compounds.[1] J. Vetter, P. et al: Ageing mechanisms in lithium-ion batteries, J. Power Sources, 2005, 147, 269–281.[2] D. Castelvecchi: Electric cars: the battery challenge, Nature, 2021, 596, 336–339.[3] P. G. Bruce et al: Li-O2 and Li-S batteries with high energy storage, Nat. Mater., 2012, 11, 19–29.[4] S. Zhang et al: Recent advances in electrolytes for lithium-sulfur batteries, Adv. Energy Mater., 2015, 5, 1–28.[5] Y. Tsao et al: Designing a quinone-based redox mediator to facilitate Li2S oxidation in Li-S batteries, Joule, 2019, 3, 872–884.

Synthesis of Nixp/C Nanofibers As Interlayer and Sulfur Host for Lithium-Sulfur Batteries

Lithium-sulfur batteries (LSB) have a high theoretical capacity (1675 mAh g − 1) and energy density (2600 Wh kg−1), making them one of the most promising energy storage systems. 1 However, it has some limitations, such as “shuttle effect” of polysulfides and high volume expansion, causing poor cycle performance of the battery.The transition metal phosphides with carbon materials as sulfur host for LSB have attracted extensive scientific focus due to the large surface area and strong chemisorption ability. Moreover, high electrical conductivity of carbon-based material and the chemical adsorption effect of Ni-P phase can reduce the “shuttle effect”, and improve the cyclability of the material. 2,3 In this work, nickel phosphide carbon composite (NixP/C) nanofibers were synthesized using a water-soluble carbon source polyvinylpyrrolidone (PVP) and cost-effective electrospinning method. The impact of humidity on the physical and electrochemical characteristics of the electrospun NixP/C nanofibers was studied, utilizing them as interlayer and sulfur host material for LSB.The NixP/C nanofibers were synthesized using an electrospinning machine from PVP, nickel nitrate hexahydrate, and phosphoric acid as precursors. The nanofibers were electrospun at 18 kV voltage and 0.8 mL h–1 flow rate. The electrospinning humidity (RH) varied between 19-35%. Obtained nanofibers were dried at 110 ºC for 11 h. Finally, prepared fibers were annealed at 700 ºC for 1 h with a heating rate of 5 ºC min-1 in the N2 + H2 (4%) atmosphere.The crystalline phases of the final products were observed using X-Ray diffraction (XRD, Miniflex, Rigaku). The microstructure was studied by transmission electron microscopy (TEM, JEM-1400 Plus, JEOL). According to the results shown in Figure 1, Ni2P with a hexagonal structure and the space group of P62m, and Ni12P5 with a tetragonal structure, space group of 87:I4/m were formed. Nanoparticles of NixP are uniformly distributed within the carbon fiber matrix (inset).The NixP/C freestanding mats were embedded as a sulfur host or interlayer for LSB in CR2032 coin-type cells. 1 M Li2S6 catholyte solution and 1 M LiTFSI in 1,3- dioxolane (DOL)/1,2 dimethoxyethane (DME) (v/v, 1:1) with 2 wt% of LiNO3 were used as a source of sulfur and electrolyte, respectively. Further details and obtained results will be presented at the conference. Acknowledgements This research was funded by the projects AP13068219 “Development of multifunctional free-standing carbon composite nanofiber mats”, and AP19675260 “Development of nanofibrous electrode materials for next-generation lithium-ion batteries” from the Ministry of Education and Science of the Republic of Kazakhstan.

Conversion Electrodes for Rechargeable Li-Sulfur, Na-Ion and Zn-Air Batteries

Rechargeable batteries are reliable and highly efficient energy storage devices providing high energy density at high voltages with the lead of the Li-ion technology since the early 1990s. Despite these promising advantages, the strongly limited abundance of Li and also that of other elements contained in a Li-ion battery (LIB) leads to the search for low-cost and more abundant alternatives. Especially for stationary storage devices alternative battery technologies are required. Alternative chemistries, such as those based on lithium conversion or alloying, can actually lead to higher energy density compared to the lithium (de)intercalation one.Among them, the lithium-sulfur (Li/S) conversion process appeared as one of the most promising candidates to achieve a lithium battery with enhanced performances compared to the state-of-art. In fact, sulfur electrode can deliver in lithium cell a theoretical capacity and energy density as high as 1675 mAh gS −1 and 2600 Wh kg−1 Unfortunately, soluble polysulfides can migrate and directly react with the lithium anode or shuttle between anode and cathode throughout a continuous process without any charge accumulation. This leads to efficiency decrease, active material loss or even to short circuits and cell failure, whilst insoluble polysulfides can precipitate into the cell and cause resistance increase and capacity fading. The characteristic electrochemical process involving at the cathode side the electro-deposition/dissolution of soluble species focused the attention on the nature of the current collector. Hence, flat and thin metal supports (e.g., bare Al current collector) may lead to poor performances due to high overall impedance of the cell and modest ability in allowing the complex multi-step reaction pathway, whilst thicker porous supports (e.g., gas diffusion layer, GDL) can enhance the cell response, reduce the impedance and actually boost the kinetics of the Li/S process, but suffer from its higher thickness, lowering down the volumetric energy density of the overall cell.In this view, graphene-based materials can actually allow the thinnest configuration of a carbon-coated metal support and hold, at the same time, a suitable Li/S process due to their characteristic morphology, mechanical stability and enhanced electronic conductivity. In regard to this, research activities are going to be presented about an exploited binder-free few layer graphene (FLG) thin carbon-coated Aluminum support for application in a Li/S cell with excellent characteristics in terms of stability, efficiency and delivered capacity.Conversion electrodes play also an important role for sodium-ion batteries (SIBs) being a promising alternative, since Na cells show similar properties to the Li analogues in many cases, while they are based on more environmentally friendly and/or more abundant materials. The use of SIBs often results slightly lower energy densities and cell voltages than those of LIBs, but they still provide significantly better values than lead-acid batteries, which are currently dominating the market in terms of annually manufactured capacity. Tin (Sn) and its compounds are well investigated alloy electrodes for SIBs as tin provides a very high theoretical specific capacity of 847 mAh g−1. Sn is an example that shows even better capacity retention when used in SIBs compared to its use in LIBs. Moreover, transition metal compounds containing phosphorus (P) and/or sulfur (S) are promising conversion electrodes as well, since these elements enable high specific volumetric and/or gravimetric capacities in LIBs and SIBs.In addition to LIBs and SIBs, zinc batteries are also attracting research interest due to their environmental friendliness and their applicability with aqueous electrolytes. However, especially zinc-air batteries are well established for use as primary cells, but when considered for use as secondary cells, they suffer from their low rechargeability. Despite great research efforts to solve these problems, no established system has yet been able to achieve reasonable rechargeability in the context of using the commonly considered alkaline electrolytes. However, Sun et al. (2021) found a promising approach using Zn(OTf)2 salt in a small amount of water as an electrolyte. This approach enables the formation of zinc peroxide (ZnO2) instead of formation the irreversible zinc oxide (ZnO) in alkaline electrolytes, which deposits on the gas diffusion layer electrode, blocking the oxygen evolution reaction. ZnO2, on the other hand, has been shown to be highly reversibly malleable. In our current project WaZABi, we are trying another approach using a freeze-cast zinc anode, which enables high porosity, and the application of a hybrid electrolyte under participance of a polymer for rechargeable high performance zinc air batteries.

Microstructure Characterizations of Electrodeposited Magnesium after Discharge/Charge Cycles for Rechargeable Magnesium Battery

Rechargeable magnesium (Mg) batteries attract lots of attention owing to their high theoretical volumetric energy density and low cost from the natural abundance of Mg. Additionally, Mg is less prone to dendrite growth during charging, improving the battery safety. While most studies of rechargeable Mg batteries focus on developing new electrolytes and their performances, the microstructure of the Mg metal anodes during discharge/charge cycles is not fully characterized. Therefore, in this report, we investigated the microstructure evolution of electrodeposited Mg after discharge/charge cycles on both a bulk Mg metal anode and a copper (Cu) current collector in an all phenyl complex (APC) electrolyte.The electrodeposited Mg on both the Mg anode and the Cu current collector at a current density of 2.25 mA/cm2 with a capacity of 1.5 mAh/cm2 show uniform distributions of Mg grains with an average grain size of about 1 to 2 μm. Subsequent Mg stripping with intermediate current density (0.75 mA/cm2) results in non-uniform discharge holes and possible local exposure of the substrate underneath, which could deteriorate the anode integrity. In contrast, the stripped electrodeposited Mg at relatively large (2.25 mA/cm2) and small (0.25 mA/cm2) discharge current densities show dense and uniform discharged holes on the surface. The microstructure evolution of the electrodeposited Mg on different substrates will be discussed based on the plating/stripping overpotentials and the interfacial impedances of the electrodeposited Mg under different conditions.

Mechanistic Understanding of the Role of Bis(4-nitrophenyl) Carbonate (BNC) As Additive on the Solvation Structure and Polysulfides Shuttling Effect Towards Capacity Improvement in Lithium-Sulfur Batteries

The lithium-sulfur (Li-S) batteries are considered as one of the most promising devices for next-generation energy storage applications, owing to its exceptional theoretical capacity and energy density. However, persistent challenges have hampered its performance, notably the sluggish polysulfides conversion kinetics and the polysulfides shuttling phenomenon. These issues lead to irreversible active material loss, rapid capacity decay, low coulombic efficiency, and a limited cycle life. This study demonstrates that bis(4-nitrophenyl) carbonate (BNC) can serve as an effective agent in anchoring dissolved polysulfides, thereby preventing their migration to the anode. Furthermore, this investigation indicates that BNC has the capability to modify the solvation structure of polysulfides in the electrolyte. The presence of 0.01M BNC induces a downfield shift in the 7Li NMR spectrum, signifying a strengthened solvation structure on Li-ion. This solvation modification results in altered kinetics, specifically a reduced Li2S2/Li2S conversion without sacrificing capacity, as confirmed by operando X-ray absorption spectroscopy (XAS). Operando Raman spectroscopy reveals the suppression of long-chain polysulfides (at 400 cm-1) and intermediate polysulfides (at 453 cm-1) with 0.01M BNC, mitigating sulfur shuttling to the anode. This observation is corroborated by X-ray fluorescence (XRF) mapping. Analysis of the corresponding X-ray absorption near-edge structure (XANES) demonstrates that both anodes and cathodes with 0.01M BNC exhibit lower levels of unconverted polysulfides over extended cycles. This improvement is attributed to the kinetic consequences resulting from solvation structure alteration. However, this investigation cautions against an indiscriminate increase in BNC concentration, as higher concentrations may lead to the over-conversion of soluble polysulfides. This nuanced understanding of the solvation structure's intrinsic mechanism, coupled with chemical reactions, provides valuable insights for practical design of Li-S batteries Figure 1

The Impact of Biomass-Derived Graphene-like Porous Carbon Decorated with NiO Nanoparticles on the Electrochemical Performance of Lithium-Sulfur Batteries

Lithium-sulfur batteries are considered a promising next-generation energy storage system, boasting high theoretical capacity and energy density, approximately double that of LiBs [1,2]. However, challenges such as low sulfur conductivity, significant volume expansion during cycling, and the lithium polysulfides shuttle effect hinder their practical use [3]. These issues result in side reactions, irreversible loss of active material, and anode degradation, leading to a rapid decline in cell capacity stability [4].In this research, we successfully developed a sulfur cathode carbon matrix and separator modifier from rice husk through carbonization and thermal activation. The resulting graphene-like porous carbon (GPC) exhibited high efficiency as a sulfur host, enhancing the electrochemical performance of the cathode. The GPC-NiO composite also served effectively as a separator modifier, catalyzing lithium polysulfides' redox reactions and improving the overall cycling stability of lithium-sulfur batteries. In particular, the GPC@S/GPC-NiO-20 cell demonstrated an excellent initial discharge capacity of 1519 mAh g-1 at 0.2 C. Also, it delivered excellent long-term cycling, maintaining a discharge capacity of 661 mAh g-1 even after 400 cycles at 1 C, with a Coulombic efficiency exceeding 97%. It exhibited a promising rate capability of 568 mAh g-1 at 2 C and retained a discharge capacity of 603 mAh g-1 over 100 cycles at 0.2 C with a sulfur loading of 4.0 mg cm-2. Acknowledgments This research is funded by the Science Committee of the Ministry of Science and Higher Education of the Republic of Kazakhstan (Grant No. AP19677708).

Bioinspired Multifunctional Nanocomposites for Energy Storage Applications

Bioinspired ion transport membranes have been extensively researched for energy storage applications. Sulfur, due to its natural abundance, low toxicity, high theoretical specific energy density (2600 Wh/kg), and high specific capacity (1675 mA/g), is attracting significant attention as an alternative battery system to replace traditional lithium-ion batteries that have limitations in terms of safety, capacity, and energy density in various applications. However, polysulfide dissolution and shuttling pose challenges that prevent the mass commercialization of metal sulfur batteries. We have developed a practical and comprehensive approach for developing high-performance metal sulfur batteries inspired by biological ion transport mechanisms. We used aramid nanofiber (ANF)-based composite ion transport membranes that prevent dendrite formation and confine polysulfides on the cathode side. ANF composite battery separators provide diverse and opposing properties, including high mechanical properties, high ionic conductivity, and high thermal/chemical stability. These biomimetic separators have highly selective ion-sieving properties that make the batteries safe and high-performing. It is crucial to fabricate such biocompatible, affordable, flexible, and high-energy-density batteries to power next-generation electronics such as portable, wearable, and implantable biomedical devices.

Single Atom Catalyst Anchored on Nitrogen-Doped Porous Carbon As an Effective Sulfur Host for Lithium-Sulfur Batteries

Lithium-sulfur batteries (LSBs) are considered highly promising for next-generation energy storage due to their high theoretical specific capacity and energy density. However, challenges such as the insulating nature of sulfur cathodes, the detrimental shuttle effect of lithium polysulfides (LiPSs), and sluggish conversion kinetics of LiPSs during charge/discharge cycles impede their commercial viability. In this study, we employed a facile ‘dissolution-carbonization’ approach to synthesize nitrogen-coordinated monometallic atomic catalysts anchored on mesoporous carbon to promote surface-mediated reactions of LiPSs. The hierarchical porous carbon support physically confines the sulfur species, while the introduction of single atoms efficiently captures polysulfide intermediates and facilitates their redox conversion kinetics with a lower activation energy barrier. The synergistic effect of the single atom and nitrogen-rich porous carbon (NC) significantly enhances reaction kinetics and sulfur species utilization. Consequently, LSBs incorporating single-atom catalysts (SACs) demonstrate remarkable performance metrics, including high-capacity retention (824.2 mAh g−1), superior Coulombic efficiency (>98.5%), low-capacity decay rate (0.042% per cycle) after 500 cycles at 1 C, and excellent rate capability (776 mA h g–1 at 3 C). This work presents an effective strategy that combines the functions of a nanoporous material host and SACs for lithium-sulfur batteries.

Microstructure Evolution of Electrodeposited Magnesium on Copper Current Collector during Cycles for Anode-Free Rechargeable Magnesium Battery

Rechargeable magnesium (Mg) batteries attract lots of interest owing to their high theoretical volumetric energy density and low cost from the natural abundance of Mg. Additionally, Mg is less prone to dendrite growth during charging, which improves the battery safety. However, rechargeable Mg battery systems suffer from sluggish reaction kinetics on the electrodes and poor cycle life, greatly limiting their practical competitiveness. While most studies of rechargeable Mg batteries focus on the development of electrolytes and their feasibilities, the microstructure evolution of the Mg metal anodes during cycles is not fully unveiled. Furthermore, when using Mg metal as the anode, the excessive Mg may limit the overall energy density of the cells. Recently, anode-free battery systems were introduced to further improve the battery capacity. In this report, we investigated anode-free rechargeable magnesium batteries by electrodepositing Mg on a copper (Cu) current collector in an all phenyl complex (APC) electrolyte. Afterward, the microstructure evolution of the electrodeposited Mg after discharge/charge cycles was studied.The electrodeposited Mg on the Cu current collector with a current density of 2.25 mA/cm2 and a capacity of 1.5 mAh/cm2 shows a uniform distribution of Mg grains with an average grain size of 1.14 ± 0.06 μm. Subsequent Mg stripping with half the deposited capacity (0.75 mAh/cm2) was conducted at various current densities. Stripping with intermediate current density (0.75 mA/cm2) results in non-uniform discharge holes and possible local exposure of the Cu current collector, which could deteriorate the anode integrity. In contrast, the stripped electrodeposited Mg at relatively large (2.25 mA/cm2) and small (0.25 mA/cm2) discharge current densities show dense and uniform discharged holes on the surface. After prolonged discharge/charge cycles at a relatively large current density (2.25 mA/cm2), the electrodeposited Mg still exhibits a uniform surface morphology. In addition to cycling the electrodeposited Mg, a Mg-sulfur (Mg-S) full cell was also assembled with an anode of electrodeposited Mg on Cu and a sulfur/graphite cathode to explore the potential of anode-free rechargeable Mg-S battery. Figure 1