Sodium-sulfur Batteries Research Articles

In Situ Electrochemical Evolution of Amorphous Metallic Borides Enabling Long Cycling Room-/Subzero-Temperature Sodium-Sulfur Batteries.

Room temperature sodium-sulfur batteries (RT Na-S) have garnered significant attention for their high energy density and cost-effectiveness, positioning them as a promising alternative to lithium-ion batteries. However, they encounter challenges such as the dissolution of sodium polysulfides and sluggish kinetics. Introducing high-activity electrocatalysts and enhancing the density of active sites represents an efficient strategy to enhance reaction kinetics. Here, an amorphous Ni-B material that undergoes electrochemical evolution to generate the NiSx phase within an operational sodium-sulfur battery, contrasting with the crystalline NiB counterpart is fabricated. Electrochemical cycling facilitated the establishment of an interface between the amorphous Ni-B and NiSx, leading to heightened catalytic activity and improved reaction kinetics. Consequently, batteries utilizing the amorphous Ni-B showcased a notable initial specific capacity of 1487 mAh g-1 at 0.2 A g-1, exhibiting exceptional performance under high current densities of 5 A g-1, in low-temperature conditions (-10°C), with high sulfur loading, and in pouch cell configurations.

Sustainable Sulfur-Carbon Hybrids for Efficient Sulfur Redox Conversions in Nanoconfined Spaces.

Nanoconfinement is a promising strategy in chemistry enabling increased reaction rates, enhanced selectivity, and stabilized reactive species. Sulfur's abundance and highly reversible two-electron transfer mechanism have fueled research on sulfur-based electrochemical energy storage. However, the formation of soluble polysulfides, poor reaction kinetics, and low sulfur utilization are current bottlenecks for broader practical application. Herein, a novel strategy is proposed to confine sulfur species in a nanostructured hybrid sulfur-carbon material. A microporous sulfur-rich carbon is produced from sustainable natural precursors via inverse vulcanization and condensation. The material exhibits a unique structure with sulfur anchored to the conductive carbon matrix and physically confined in ultra-micropores. The structure promotes Na+ ion transport through micropores and electron transport through the carbon matrix, while effectively immobilizing sulfur species in the nanoconfined environment, fostering a quasi-solid-state redox reaction with sodium. This translates to ≈99% utilization of the 2e- reduction of sulfur and the highest reported capacity for a room temperature Na-S electrochemical system, with high rate capability, coulombic efficiency, and long-term stability. This study offers an innovative approach toward understanding the key physicochemical properties of sulfurcarbon nanohybrid materials, enabling the development of high-performance cathode materials for room-temperature Na-S batteries with efficient sulfur utilization.

Phosphorus and Nitrogen Dual-Doped Hollow Porous Carbon Spheres toward Enhanced Cycling Stability of Room-Temperature Na-S Batteries.

Development of room-temperature sodium-sulfur (RT Na-S) batteries with satisfactory cycling life and rate capability remains challenging due to the unfavorable electric conductivity from S species, sluggish redox kinetics of S conversion, and serious shuttle effects of sodium polysulfides (NaPSs). To address these issues, a phosphorus and nitrogen dual-doped hollow porous carbon sphere (PN-HPCs) is synthesized as the S hosts, which enhances the electric conductivity, ion diffusion, and conversion of polysulfides. Such a hollow hierarchically porous structure is beneficial to accommodate the volume variations of S species and shorten the ion/electron transfer distances during electrochemical reaction process. As a result, the S@PN-HPCs600 cathode delivers noticeable cycling performance (313 mAh g-1 after 4500 cycles at 5.0 C, and capacity degeneration of only 0.01% per cycle) and rate capability (646.4 mAh g-1@1.0 and 527.5 mAh g-1@3.0 C). This work presents an efficient strategy based on structural confinement and dual-heteroatom doping engineering for long-life RT Na-S batteries.

Low‐Temperature Sodium–Sulfur Batteries Enabled by Ionic Liquid in Localized High Concentration Electrolytes

AbstractLow ionic migration and compromised interfacial stability pose challenges for low‐temperature batteries. In this work, we discovered that even with the state‐of‐the‐art localized high‐concentration electrolytes (LHCEs), uncontrolled Na electrodeposition occurs with a huge overpotential of >1.2 V at −20 °C, leading to cell failure within tens of hours. To address this, we introduce a new electrolyte category that incorporates an ionic liquid as a key solvation species. Diverging from traditional LHCEs, the IL‐tailored LHCE facilitates an anion–solvent‐molecules exchange within the solvation sheath between Na+ and organic cations at low temperatures. This behavior reduces solvation cluster size and strengthens Na+–anion coordination, which proves instrumental in enabling fast ionic dynamics in both the bulk liquid and at the interface. Therefore, durable Na electrodeposition and shuttle‐free, 0.5 Ah sodium–sulfur pouch cells are achieved at −20 °C, for the first time, surpassing the limitations of typical LHCEs. This tailoring strategy opens a new design direction for advanced batteries operating in fast‐charge and wide‐temperature scenarios.

Evaluation of new Garima data using type-II generalized progressive-hybrid technique and its application to a sodium–sulfur battery

In recent years, several novel modeling applications have been able to better fit complex datasets, and they can provide insights that would not be possible with traditional distributions. A new model developed by mixing the exponential and gamma models, called the Garima model, is discussed in this article. This model exhibits a better behavior fit than exponential and Lindley, among others. When the reliability practitioner wishes to score a specific number of failed units, a generalized progressive-hybrid-censored Type-II technique has been proposed to reduce both the length and expense of a life test. Given the availability of the presented data, the difficulty of estimating the scale parameter and various reliability time aspects of the Garima model is investigated using likelihood and Bayes inferential approaches. In addition, when the Garima parameter is assumed to have gamma density prior, the Markovian-Chain via Monte-Carlo sampler from a symmetric loss is performed to obtain the symmetric Bayes’ infer. Besides the asymptotic confidence intervals, the highest intervals for all unknown subjects are also developed. Simulation comparisons are also carried out, and useful recommendations are provided. A real data application is examined based on genuine datasets from the physical sector to see how the examined approaches may be implemented in real-life situations.

Promoting Cathodic Kinetics and Anodic Stability in Practical Room-Temperature Sodium-Sulfur Batteries with Bifunctional Electrolytes.

The development of room-temperature (RT) sodium-sulfur (Na-S) batteries is severely hindered due to the slow kinetics of the S cathode and the instability of the Na-metal anode. To overcome this, we introduced a dual-functional electrolyte cosolvent, trifluoromethanesulfonamide (TFMSA). Short-chain Na2Sx (1 ≤ x ≤ 2) can be effectively dissolved due to the strong H-S bond interaction between TFMSA and sulfides, which changes the S conversion process, thereby effectively enhancing the conversion kinetics of the cathode. Meanwhile, TFMSA can generate a stable solid electrolyte interphase on the Na-metal surface to protect it from soluble polysulfide attack. Therefore, the RT Na-S batteries using the ether electrolyte show a high initial discharge capacity of 896.6 mAh g-1 and a capacity retention rate of 73% after 150 cycles at 0.2C, and the pouch cell also demonstrates its practical performance. This work proposes a dual-functional electrolyte cosolvent selection principle to inspire the practical application of high-performance RT Na-S batteries.

Fluorinated ester additive to regulate nucleation behavior and interfacial chemistry of room temperature sodium-sulfur batteries

Room temperature sodium-sulfur (RT Na-S) batteries are considered as advanced energy storage technology due to their low cost and high theoretical energy density. However, challenges such as the growth of sodium dendrite and dissolution of sodium polysulfides significantly hinder the electrochemical performance. Herein, we developed a propylene carbonate (PC)-based electrolyte with Methyl 2-Fluoroisobutyrate (MFB) as an additive. The ester group in the MFB additive is capable of participating in and reconfiguring the coordination of their Na+ solvated structures, thereby lowering the desolvation barrier and regulating the Na anode’s interfacial reaction and nucleation behavior. The polar C−F bond at the other end helps to reduce the lowest unoccupied molecular orbital (LUMO) energy of the MFB additive, enabling the preferential decomposition of MFB to form the F-rich inorganic phase strong polar solid electrolyte interphase (SEI), contributing to the inhibition of Na dendrite growth, the accumulation of dead Na. In addition, NaF-riched cathode electrolyte interphase (CEI) was also observed on sulfur-based cathode, which can effectively inhibited the shuttle effect. Consequently, the developed RT Na-S battery exhibit excellent electrochemical performance.

Inhibiting Shuttle Effect and Dendrite Growth in Sodium-Sulfur Batteries Enabled by Applying External Acoustic Field.

The room-temperature sodium-sulfur (RT Na-S) battery is a promising alternative to traditional lithium-ion batteries owing to its abundant material availability and high specific energy density. However, the sodium polysulfide shuttle effect and dendritic growth pose significant challenges to their practical applications. In this study, we apply diverse disciplinary backgrounds to introduce a novel method to stimulate polarized BaTiO3 (BTO) nanoparticles on the separator. This approach generates more charges due to the piezoelectric effect under stronger driving forces produced by applying a controllable acoustic field at the outer edge of the cell. The acoustically stimulated BTO attracts more polysulfides, thus reducing the shuttling effect from the cathode to the anode and ultimately enhancing the battery performance. Meanwhile, the acoustic waves create additional streaming flows, improving the uniformity of the sodium ion dispersion, enhancing the sodium ion transport and reducing the possibility of sodium dendrite development. We believe that this work offers a new strategy for the development of high-performance Na-S batteries.

N/O dual coordination of cobalt single atom for fast kinetics sodium-sulfur batteries

N/O dual coordination of cobalt single atom for fast kinetics sodium-sulfur batteries

Stable Dendrite-Free Room Temperature Sodium-Sulfur Batteries Enabled by a Novel Sodium Thiotellurate Interface.

The practical application of room-temperature sodium-sulfur (RT Na-S) batteries was severely hindered by inhomogeneous sodium deposition and notorious sodium polysulfides (NaPSs) shuttling. Herein, novel sodium thiotellurate (Na2TeS3) interfaces are constructed both on the cathode and anode for Na-S batteries to simultaneously address the Na dendritic growth and polysulfide shuttling. On the cathode side, a heterostructural sodium sulfide/sodium telluride embedded in a carbon matrix (Na2S/Na2Te@C) was rationally designed through a facile carbothermal reaction, where the Na2TeS3interface will be in-situ chemically obtained. Such an interface provides abundant electron/ion diffusion channels and ensures rich catalytic surfaces toward Na-S redox, which could significantly improve the utilization of active material and alleviate polysulfide shuttling in the cathode. On the anode side, the inevitable formation of soluble polytellurosulfides species will migrate on Na anode surface, finally constructing a compact and smooth solid-electrolyte Na2TeS3 interphase (SEI) layer. Such electrochemical formed Na2TeS3 interface can significantly enhance ionic transport and stabilize Na deposition, thus realizing dendrite-free Na-metal plating/stripping. Benefitting from these advantages, an anode-free cell fabricated with the Na2S/Na2Te@C cathode exhibits an ultrahigh initial discharge capacity of 634 mAh g-1 at 0.1 C, which could pave a new path to design high-performance cathodes for anode-free RT Na-S batteries.

The design of chemisorption and catalysis synergistic defender for efficient room temperature sodium-sulfur batteries

Room temperature sodium-sulfur (RT-Na/S) batteries are a promising candidate for large-scale energy storage systems owing to their low manufacturing cost and high energy density. However, the severe shuttle effects and sluggish reaction kinetics hinder their practical application. Here, a Fe3Se4 nanoparticle anchored three-dimensional nitrogen-doped porous carbon nanosheet was designed as a functional defender to inhibit the shuttle effect and achieve high sulfur utilization. The porous carbon nanosheet builds a fast platform for electron and ion transport and acts as a limiting barrier for polysulfide dissolution and shuttling. Additionally, Fe3Se4 nanoparticles are incorporated to enhance the chemical anchoring and catalytic activity of polysulfides. The ex-situ characterization revealed that the Fe sites can feed electrons to polysulfides, thus facilitating the conversion of long-chain polysulfides to Na2S, resulting in high sulfur availability (323 mAh/g at 2 A/g) and long-term cycle life (72 % capacity retention at 1 A/g for 500 cycles).

Nature-Derived Sulfur Carbons for Highly-Efficient Room Temperature Sodium-Sulfur Energy Storage

In recent years, a growing interest in “beyond-Li-ion“ batteries has caused a speedy development of alternative battery technologies based on other alkali metals. Room temperature sodium sulfur (RT Na-S) batteries are potential candidate for sustainable large-scale energy storage systems. They offer low cost, nontoxicity and natural abundance of both cathode and anode materials combined with high theoretical energy density. However, rapid capacity fading related to the irreversible shuttling of soluble polysulfides, poor reaction kinetics and low sulfur utilisation in the cathode materials significantly limit their practical application.In this work, a microporous sulfur-carbon complex is produced from sustainable natural precursors in a one-pot synthesis via stepwise thermally-induced inverse vulcanisation and condensation. The material exhibits a unique structure, with sulfur chains covalently anchored to the conductive carbon matrix and physically confined in ultra-micropores. An increase in sulfur content in the sulfur-copolymer alters the morphology and chemical composition of the final sulfur-carbon material, enhancing the amount of long-chain sulfur. The combination of optimal microstructure, good electrical conductivity and high content of electrochemically active sulfur translates to an unprecedented ~99% utilisation of sulfur and the highest reported capacity for a room temperature Na-S cathode, along with high rate capability, coulombic efficiency and long-term stability. This study offers an innovative approach towards the understanding of the key chemico-physical properties of the sulfur-carbon composite materials for the development of high-performance cathodes in RT Na-S batteries with an atom-efficient utilisation of sulfur.

Chitin-Derived Hierarchical Meso- and Microporous Carbon Enables High-Rate Sulfur Cathode of Sodium-Sulfur Batteries.

Room temperature Na-S batteries are considered as a promising alternative energy storage system because of their abundant material resources and high theoretical energy density. However, the severe polysulfide shuttle effect and slow reaction kinetics hinder their practical application. Herein, a hierarchical meso- and microporous carbon with nitrogen self-doping (NSPC) is prepared using chitin as the carbon precursor and serves as a novel host to confine the sulfur (S⊂NSPC). An optimized structure of NSPC, including abundant graphite nanocrystals, large pore volume of 1.76 cm3 g-1, and large specific surface area of 2073 m2 g-1 is obtained at the carbonization temperature of 1000 °C. These merits contribute to significantly enhanced charge transfer and ion diffusion of the as-prepared S⊂NSPC-1000 cathode, which exhibits the outstanding sodium storage performance, including high reversible capacities of 1207 mAh g-1 at 0.1 C and 891 mAh g-1 at 2 C and stable cycling with a low capacity decay for 400 cycles at 1 C, among other S⊂NSPC cathodes and previously reported cathodes for Na-S batteries. This cathode can also afford stable cycling at a high sulfur loading.

A smart building energy management incorporating clustering-based tariffs in the presence of domestic solar energy, battery, and electric vehicle

Smart buildings play a crucial role in optimizing energy management within the power network. As end-users of the power network, they have the ability to not only reduce economic costs for householders but also modify the technical indices of the power network. To promote efficient device management in smart homes (SH), demand response programs are recommended for consumers. This research investigates the application of clustering-based electricity pricing strategy aimed at effectively managing the energy devices of a residential smart home. The utilized method categorizes the electricity tariff into five rates according to the clustering of the real-time pricing program. Ward’s clustering method is utilized to cluster and determine new electricity tariffs. The primary goal of the energy management program is to minimize the building’s energy cost, which is accomplished through the utilization of the multi-verse optimizer. The smart home consists of essential and manageable appliances, a photovoltaic panel (PV), a sodium-sulfur (NaS) battery, and an electric vehicle (EV). The initial parameters of the PV and EV are modeled stochastically by their probability distribution functions and calculated using the Latin hypercube sampling algorithm. The smart building’s performance is assessed by taking into account various demand response programs. The numerical results present that the application of the clustering-based management method has resulted in a significant reduction of 23–43 % in the electricity cost of smart homes. Additionally, the smart home exhibits a more linear consumption pattern when considering the electricity tariffs based on the clustering approach.

Tellurium doped sulfurized polyacrylonitrile nanoflower for high-energy-density, long-lifespan sodium-sulfur batteries

Sodium-sulfur (Na−S) batteries are promising energy storage devices for large-scale applications due to their high-energy-density and abundant material reserve. However, the practical implementation of room temperature (RT) Na−S batteries faces challenges, including low-energy-density and limited lifespan, particularly attributed to the properties of sulfurized polyacrylonitrile (SPAN). In this study, we address these challenges by introducing tellurium doping into SPAN nanoflowers, enhancing their performance for Na−S batteries. The resulting material exhibits high sulfur loading as well as superior electron and ion transport properties, leading to enhanced redox kinetics and improved battery performance. The tellurium-doped SPAN nanoflower electrode delivers an exceptional composite capacity of 700 mAh g−1 at 0.1 C and demonstrates stable cycling over 2400 cycles with minimal capacity fade (0.01 % average fading rate). Even under challenging conditions (24.0 mg cm−2, E/S=5 mg μLS−1, N/P=2.1), the Na−S battery achieves a high areal capacity of 16.1 mAh cm−2, resulting in an impressive energy density of 340.9 Wh kg–1 based on cathode and anode. This work presents a promising approach to designing high-energy-density, long-lifespan RT Na−S batteries, with potential applications for other metal-sulfur battery systems.

Amorphous FeSnOx Nanosheets with Hierarchical Vacancies for Room-Temperature Sodium-Sulfur Batteries.

Room-temperature sodium-sulfur (RT Na-S) batteries, noted for their low material costs and high energy density, are emerging as a promising alternative to lithium-ion batteries (LIBs) in various applications including power grids and standalone renewable energy systems. These batteries are commonly assembled with glass fiber membranes, which face significant challenges like the dissolution of polysulfides, sluggish sulfur conversion kinetics, and the growth of Na dendrites. Here, we develop an amorphous two-dimensional (2D) iron tin oxide (A-FeSnOx) nanosheet with hierarchical vacancies, including abundant oxygen vacancies (Ovs) and nano-sized perforations, that can be assembled into a multifunctional layer overlaying commercial separators for RT Na-S batteries. The Ovs offer strong adsorption and abundant catalytic sites for polysulfides, while the defect concentration is finely tuned to elucidate the polysulfides conversion mechanisms. The nano-sized perforations aid in regulating Na ions transport, resulting in uniform Na deposition. Moreover, the strategic addition of trace amounts of Ti3C2 (MXene) forms an amorphous/crystalline (A/C) interface that significantly improves the mechanical properties of the separator and suppresses dendrite growth. As a result, the task-specific layer achieves ultra-light (~0.1 mg cm-2), ultra-thin (~200 nm), and ultra-robust (modulus=4.9 GPa) characteristics. Consequently, the RT Na-S battery maintained a high capacity of 610.3 mAh g-1 and an average Coulombic efficiency of 99.9 % after 400 cycles at 0.5 C.

Effective Liquid Electrolytes for Enabling Room‐Temperature Sodium–Sulfur Batteries

AbstractGlyme‐based electrolytes for sodium‐sulfur (Na–S) batteries are proposed for advanced cell configuration. Solutions of NaClO4 or NaCF3SO3 in tetraglyme are investigated in terms of thermal stability, ionic conductivity, Na+‐transference number, electrochemical stability, stripping‐deposition ability, and chemical stability in Na‐cells. Subsequently, versions of the electrolytes doped with fluoroethylene carbonate (FEC) are prepared using 0.5, 1, 2, or 3% additive weight concentrations, and evaluated by adopting the same approach used for the bare solutions. Scanning electron microscopy (SEM) provides morphological details of the passivation layer formed on the Na electrodes, while X‐ray photoelectron spectroscopy (XPS) sheds light on its composition. The most relevant achievement of the FEC‐added electrolyte is the suppression of the polysulfide shuttle in Na–S cells using a cathode with 70 wt.% of sulfur in the composite. This result appears even more notable considering the low amount of the additive requested for enabling the reversible cell operation. The solutions using 1% of FEC show the best compromise between cell performance and stability. Cyclic voltammetry (CV) displays the potential region related to the FEC electrochemical process responsible for Na–S cell operation. The understanding of the electrolyte features enables additional cycling tests using sulfur cathode with an optimized current collector, increased specific capacity, and coulombic efficiency.

An Investigation into Electrolytes and Cathodes for Room-Temperature Sodium–Sulfur Batteries

In the pursuit of high energy density batteries beyond lithium, room-temperature (RT) sodium–sulfur (Na-S) batteries are studied, combining sulfur, as a high energy density active cathode material and a sodium anode considered to offer high energy density and very good standard potential. Different liquid electrolyte systems, including three different salts and two different solvents, are investigated in RT Na-S battery cells, on the basis of the solubility of sulfur and sulfides, specific capacity, and cyclability of the cells at different C-rates. Two alternative cathode host materials are explored: A bimodal pore size distribution activated carbon host AC MSC30 and a highly conductive carbon host of hollow particles with porous particle walls. An Na-S cell with a cathode coating with 44 wt% sulfur in the AC MSC30 host and the electrolyte 1M NaFSI in DOL/DME exhibited a specific capacity of 435 mAh/gS but poor cyclability. An Na-S cell with a cathode coating with 44 wt% sulfur in the host of hollow porous particles and the electrolyte 1M NaTFSI in TEGDME exhibited a specific capacity of 688 mAh/gS.

A ZIF-8-enhanced PVDF/PEO blending polymer gel membrane for quasi-solid-state Na-S batteries with long cycling lifespan

Ambient-temperature sodium-sulfur (Na-S) battery with high energy density and low cost has been considered as the promising energy density system. However, its commercial application is limited by the rapid capacity decay of the sulfur electrode and the instability of sodium dendrites with the safety issues. Herein, a ZIF-8 enhanced PVDF/PEO blending polymer gel membrane (PPZ) is reported for stable and safe quasi-solid-state Na-S battery with sulfurized polyacrylonitrile (SPAN) cathode and Na metal anode. The optimized gel polymer membrane with the dense framework exhibited the rapid Na+ migration, superior mechanical property with the tensile strength of 16.5 MPa and the elongation-at-break of 171 %, which is conductive to regulate the Na+ ion flux with the uniform Na plating and prevent the dendritic growth. The assembled symmetric Na/PPZ-GPE/Na cell delivered the stable cycling for 250 h with almost constant voltage hysteresis of 150 mV. Benefited from the superior interfacial stability between PPZ-GPE and Na as well as PPZ-GPE and SPAN, the SPAN/PPZ-GPE/Na cell exhibited the high capacity of 1585.4 mA h g−1 with the capacity retain of 97 % of third cycle after 465 cycles. This work offers exemplary electrolyte design that concurrently and effectively tackles the problems in Na-S battery and presents an excellent quasi-solid sodium-sulfur battery with the high capacity and long cycling.

Synergistically promoting the catalytic conversion of polysulfides via in-situ construction of Ni-MnO2 heterostructure on N-doped hollow carbon spheres towards high-performance sodium-sulfur batteries

The room-temperature sodium-sulfur (RT Na-S) battery is considered to be a highly promising electrochemical energy storage device, attributed to its high energy density, rich sulfur reserve, and nontoxicity. However, it is constrained by the polysulfide shuttling and the low intrinsic conductivity of active sulfur. A sacrificial template method has been used to develop hetero-structured Ni-MnO2 embedded in micro/mesoporous hollow carbon spheres (HCS@Ni-MnO2) to overcome these challenges. As evidenced by electrochemical properties and computational results, the construction of hetero-structured Ni-MnO2 provides a strong affinity to polysulfides. Meanwhile, the highly conductive in-situ constructing Ni-MnO2 structure has strong adsorption to soluble sodium polysulfides and effectively improves the catalytic conversion. The micro- and mesoporous hollow carbon sphere improves the reactivity of the sulfur cathodes and physically suppresses polysulfides shuttling. Befitting from the physical and chemical confinement and the fast redox reaction of polysulfides, the as-prepared S/HCS@Ni-MnO2 cathode exhibits a high capacity of 1031.7 mAh g−1 at 0.2 A g−1 after 100 cycles, surpassing the capacities of S/HCS@Ni (820.3 mAh g−1), S/HCS@MnO2 (942.4 mAh g−1) and S/HCS (866.7 mAh g−1). Moreover, the battery with S/HCS@Ni-MnO2 cathode also exhibits excellent cycle life (586.8 mAh g−1 at 5 A g−1 after 1000 cycles) and a high rate performance (553.8 mAh g−1 at 10 A g−1). This study provides an efficient strategy for synthesizing multiple compound hetero-structured materials to facilitate the development of energy storage applications.