Temperature 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.

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.

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.

A Polysulfides‐Defensive, Dendrite‐Suppressed, and Flame‐Retardant Separator with Lean Electrolyte for Room Temperature Sodium–Sulfur Batteries

AbstractThe dissolution/shuttling of sodium polysulfides, coupled with sodium dendrites growth, severely compromises the lifespan and stability of room temperature sodium–sulfur (RT Na–S) batteries. Herein, it proposes employing a functionalized porous ZIF‐based membrane (PZM) to address these two challenges. First, the metal ions embedded within the zeolitic imidazolate framework chemically bind with polysulfide anions, curtailing their detrimental shuttling. Second, the tailored porous structure of the membrane ensures a selective and uniform pathway for sodium ions, significantly reducing non‐uniform deposition and curbing dendritic sodium growth. Third, the intrinsically non‐combustible nature of the ZIF‐based membrane acts as a fortification against thermal outbursts and electrolyte decomposition. Implementing this polysulfide‐resistant, dendrite‐inhibiting and flame‐retardant PZM with a standard S/C cathode leads to the creation of a robust separator with lean electrolyte RT Na–S battery. This configuration may impart a novel perspective for the advancement and enhancement of RT Na–S battery systems.

Understanding the charge transfer effects of single atoms for boosting the performance of Na-S batteries.

The effective flow of electrons through bulk electrodes is crucial for achieving high-performance batteries, although the poor conductivity of homocyclic sulfur molecules results in high barriers against the passage of electrons through electrode structures. This phenomenon causes incomplete reactions and the formation of metastable products. To enhance the performance of the electrode, it is important to place substitutable electrification units to accelerate the cleavage of sulfur molecules and increase the selectivity of stable products during charging and discharging. Herein, we develop a single-atom-charging strategy to address the electron transport issues in bulk sulfur electrodes. The establishment of the synergistic interaction between the adsorption model and electronic transfer helps us achieve a high level of selectivity towards the desirable short-chain sodium polysulfides during the practical battery test. These finding indicates that the atomic manganese sites have an enhanced ability to capture and donate electrons. Additionally, the charge transfer process facilitates the rearrangement of sodium ions, thereby accelerating the kinetics of the sodium ions through the electrostatic force. These combined effects improve pathway selectivity and conversion to stable products during the redox process, leading to superior electrochemical performance for room temperature sodium-sulfur batteries.

Designing Urchin-Like S/SiO2 with Regulated Pores Toward Ultra-Fast Room Temperature Sodium-Sulfur Battery.

Captured by high theoretical capacity and low-cost, Sodium-Sulfur (Na-S) batteries have been deemed as promising energy-storage systems. However, their electrochemical properties, containing both cycling and rate properties, still suffer from the notorious "shuttle effect" of polysulfide. Herein, through the effective regulation of pore sizes, a series of S/SiO2 cathode materials are obtained. Benefitting from the abundant pore channels of SiO2 particles, the sulfur loading is as high as 76.3%. Importantly, a suitable pore size can lead to adequate reaction and rapid diffusion behaviors, resulting in excellent electrochemical performances. Specifically, at 2.0Ag-1, the initial capacity of the as-optimized sample can be up to 1370.6mAhg-1. Surprisingly, even after 1050 cycles, it could achieve a high reversible capacity of 1280.8mAhg-1 with an attenuation rate of 0.089%. At 5.0Ag-1, after 500 cycles, the capacity can still remain ≈ 1132.6mAhg-1 (capacity retention rate, 97.5%). Given this, the work is anticipated to offer an effective strategy for advanced electrodes for Na-S batteries.

Nitrogen-doped porous carbon hosted sulfur-rich polymer for room temperature Na-S batteries with superior cycle performances

Room temperature sodium-sulfur (RT Na-S) batteries are one of the most promising energy storage systems with high energy density due to the abundant reserves of sodium and sulfur elements on Earth. As a potential cathode material, sulfur-rich polymers are rarely reported in RT Na-S batteries compared with other metal-sulfur batteries. The unusual occurrence is a result of sulfur-rich polymer cathodes failing in Na-S batteries. To reverse the process, herein, we first illuminate the failure mechanism of sulfur-rich polymer cathodes (S-DIB as an example) in Na-S batteries, which root from the chemical reaction between the polysulfide and the sodium anode. To address this issue, we incorporate nitrogen-doped carbon (NC) into composites with S-DIB to establish ion diffusion pathways and limit polysulfide diffusion. The resulting S-DIB@NC composite demonstrates exceptional cycling performance, achieving a high capacity of 457 mA h g-1 after 1300 cycles. This research constitutes a significant step towards enhancing the viability of sulfur-rich polymers in Na-S batteries and paves the way for their widespread application.

Strategies to Stabilize the Sodium metal anode for High-energy Room-temperature Sodium-Sulfur Batteries

Room temperature sodium-sulfur batteries possess higher specific energy and improved inherent safety compared to their high-temperature analogs used in stationary grid storage. The viability of room temperature sodium batteries depends critically on the mechanical and ionic transport properties of the solid electrolyte interphase. Solid electrolyte interphases address a number of concomitant challenges, including large volume change, low ionic conductivity, rapid dendrite growth, and high chemical reactivity, which limit the viability of sodium anodes. In this presentation, novel strategies to stabilize the sodium metal anode are discussed that enable a high-rate cycling of sodium anodes. A solid-vapor growth approach is developed to fabricate a variety of artificial interphases directly on the surface of the sodium metal anode. As a result, the metal anode could be cycled for over 600 cycles at relatively higher currents. A room-temperature sodium-sulfur cell comprising modified sodium metal anode and sulfur cathode could be cycled for over 500 cycles with minimal capacity decay per cycle.

Intercalation-type catalyst for non-aqueous room temperature sodium-sulfur batteries

Ambient-temperature sodium-sulfur (Na-S) batteries are potential attractive alternatives to lithium-ion batteries owing to their high theoretical specific energy of 1,274 Wh kg−1 based on the mass of Na2S and abundant sulfur resources. However, their practical viability is impeded by sodium polysulfide shuttling. Here, we report an intercalation-conversion hybrid positive electrode material by coupling the intercalation-type catalyst, MoTe2, with the conversion-type active material, sulfur. In addition, MoTe2 nanosheets vertically grown on graphene flakes offer abundant active catalytic sites, further boosting the catalytic activity for sulfur redox. When used as a composite positive electrode and assembled in a coin cell with excess Na, a discharge capacity of 1,081 mA h gs−1 based on the mass of S with a capacity fade rate of 0.05% per cycle over 350 cycles at 0.1 C rate in a voltage range of 0.8 to 2.8 V is realized under a high sulfur loading of 3.5 mg cm−2 and a lean electrolyte condition with an electrolyte-to-sulfur ratio of 7 μL mg−1. A fundamental understanding of the electrocatalysis of MoTe2 is further revealed by in-situ synchrotron-based operando X-ray diffraction and ex-situ time-of-flight secondary ion mass spectrometry.

P-doped porous carbon from camellia shell for high-performance room temperature sodium–sulfur batteries

Room-temperature sodium–sulfur batteries are still hampered by severe shuttle effects and sluggish kinetics. Most of the sulfur hosts require high cost and complex synthesis process. Herein, a facile method is proposed to prepare a phosphorous doped porous carbon (CSBP) with abundant defect sites from camellia shell by oxidation pretreatment combined with H3PO4 activation. The pretreatment can introduce pores and adjust the structure of biochar precursor, which facilitates the further activation of H3PO4 and effectively avoids the occurrence of large agglomeration. Profiting from the synergistic effects of physical confinement and doping effect, the prepared CSBP/S cathode delivers a high reversible capacity of 804 mAh g−1 after 100 cycles at 0.1 C and still maintains an outstanding capacity of 458 mAh g−1 after 500 cycles at 0.5 C (1 C = 1675 mA g−1). This work provides new insights into the rational design of the microstructures of carbon hosts for high-performance room temperature sodium–sulfur batteries.

3D layered structure Ti3C2Tx MXene/Ni(OH)2/C with strong catalytic and adsorption capabilities of polysulfides for high-capacity Sodium–Sulfur battery

The room temperature sodium-sulfur battery has attracted researchers' attention due to its ultra-high energy storage capacity and extremely low cost, but its poor cycling performance and severe dissolution of sodium polysulfide hinder its practical application. Here, we report a stable MXene derived composite sulfur host material based on nickel hydroxide coated with carbon nano network, to achieve the adsorption and conversion of sodium polysulfides. Due to the physical constraints provided by the closed layered structure and the synergistic effect of MXene adsorption and Ni(OH)2catalytic activity, the shuttling effect is effectively suppressed. The ex-situ analysis of electrode after reaction shows that the composite material has strong adsorption on polysulfides. In addition, Ni(OH)2can also accelerate the reaction process from sulfur to sodium sulfide. Therefore, Ti3C2Tx/Ni(OH)2/C/S composite cathode can provide extraordinary reversible capacity 1175.3 mAh/g at 0.22C after 100 cycles and excellent long cycle stability (673.5 mAh/g at 2.2 C with a low decay rate of only 0.032% per cycle over 800 cycles).

First-Principles Investigation on Multi-Sodium Sulfide and Sodium Sulfide Clusters in Sodium-Sulfide Batteries

Room temperature sodium-sulfur batteries are expected to be widely used in large energy storage and power batteries due to their high energy density, abundant resources, and low price. However, shuttle effect of polysulfide, low reactivity of the end product, low activity of sodium sulfide, and electrode swelling are the main challenges. In order to improve the low sodium sulfide reaction performance and electrode swelling, the volume swelling of the final product sodium sulfide can be well controlled by using sodium sulfide directly as the cathode, and a special cathode structure was developed to overcome the “inert” problem of Na2S. Nevertheless, the structure, relative stability and electronic properties of (Na2S)n clusters are still uncertain so far, which is a necessary prerequisite for optimizing their properties and understanding their partitioning processes. In this paper, theoretical calculations of (Na2S)n clusters were performed to investigate the catalytic decomposition of sodium sulfide by mono-atomic catalysts, giving the energy distribution of sodium ions diffusing over FeN4 and FeN2. Together, these calculations confirm the high coordination design of mono-atomic Fe–N–C catalysts with high sulfur affinity and catalytic activity. Our work is an important step toward understanding (Na2S)n clusters and improving the performance of Na–S cells.

Growing Intact Membrane by Tuning Carbon Down to Ultrasmall 0.37 nm Microporous Structure for Confining Dissolution of Polysulfides Toward High‐Performance Sodium–Sulfur Batteries

Room temperature sodium–sulfur (Na–S) batteries are severely hampered by dissolution of polysulfides into electrolytes. Herein, a facile approach is used to tune a biomass‐derived carbon down to an ultrasmall 0.37 nm microporous structure for the first time as a cathode in sodium–sulfur batteries. This produced an intact uniform Na2S membrane to greatly confine the dissolution of polysulfides while realizing a direct solid phase conversion for complete reduction of sulfur to Na2S, which delivers a sulfur loading of 1 mg cm−2 (50 wt.%), an excellent rate capacity (933 mAh g−1 @ 0.1 A g−1 and 410 mAh g−1 @ 2 A g−1), long cycle performance (0.036% per cycle decay at 1 A g−1 after 1500 cycles), and a high energy density for 373 Wh kg−1 (0.1 A g−1) based on whole electrode weight (active sulfur loading + carbon), ranking the best among all reported plain carbon cathode‐based room temperature sodium–sulfur batteries in terms of the cycle life and rate capacity. It is proposed that the solid Na2S produced in the ultrasmall pores (0.37 nm) can be squeezed out to grow an intact membrane on the electrode surface covering the outlet of the pores and greatly depressing the dissolution effect of polysulfides for the long cycle life. This work provides a green chemistry to recycle wastes for sustainable energies and sheds light on design of a unique pore structure to effectively block the dissolution of polysulfides for high‐performance sodium–sulfur batteries.

Toward Complete Transformation of Sodium Polysulfides by Regulating the Second-Shell Coordinating Environment of Atomically Dispersed Fe.

Room temperature sodium-sulfur (RT Na-S) batteries are highly competitive as potential energy storage devices. Nevertheless, their actually achieved reversible capacities are far below the theoretical value due to incomplete transformation of polysulfides. Herein, atomically dispersed Fe-N/S active center by regulating the second-shell coordinating environment of Fe single atom is proposed. The Fe-N4S2 coordination structure with enhanced local electronic concentration around the Fermi level is revealed via synchrotron radiation X-ray absorption spectroscopy (XAS) and theoretical calculations, which can not only significantly promote the transformation kinetics of polysulfides, but induce uniform Na deposition for dendrite-free Na anode. As a result, the obtained S cathode delivers a high initial reversible capacity of 1590 mAh g-1, nearly the theoretical value. This work opens up a new avenue to facilitate the complete transformation of polysulfides for RT Na-S batteries.

A Hierarchical Hybrid MXenes Interlayer with Triple Function for Room‐Temperature Sodium‐Sulfur Batteries

AbstractRoom temperature sodium sulfur (RT Na‐S) batteries with high theoretical energy density and low cost have recently gained extensive attention for potential large‐scale energy storage applications. However, the shuttle effect of sodium polysulfides is still the main challenge that leads to poor cycling stability, which hinders the practical application of RT Na‐S batteries. Herein, a multifunctional hybrid MXene interlayer is designed to stabilize the cycling performance of RT Na‐S batteries. The hybrid MXene interlayer comprises a large‐sized Ti3C2Tx nanosheets inner layer followed by a small‐sized Mo2Ti2C3Tx nanoflake outer layer on the surface of the glass fiber (GF) separator. The large‐sized Ti3C2Tx nanosheet inner layer provides an effective physical block and chemical confinement for the soluble polysulfides. The small‐sized Mo2Ti2C3Tx outer layer offers an excellent polysulfide trapping capability and accelerates the reaction kinetics of polysulfide conversion, due to its superior electronic conductivity, large specific surface area, and Mo‐rich catalytic surfaces. As a result, RT Na‐S batteries with this hybrid MXene interlayer modified glass fiber separator deliver a stable cycling performance over 200 cycles at 1 C with an enhanced capacity retention of 71%. This unique structure design provides a novel strategy to develop 2D material‐based functional interlayer for high‐performance metal‐sulfur batteries.

Co4N embedded nitrogen doped carbon with 2D/3D hybrid structure as sulfur host for room-temperature sodium-sulfur batteries

Room temperature sodium-sulfur (RT Na-S) batteries demonstrate a high theoretical energy density, but their practical application is limited by the sodium polysulfides (NaPSs) shuttling and slow redox kinetics. Herein, we report the design of the dimensional hybrid structure of 2D ZIF-67 nanosheets and 3D ZIF-67 polyhedron on the surface of carbon fiber by a pseudomorphic replication approach. After pyrolysis in ammonia, a hybrid structure composed of 2D N-doped carbon nanosheets and 3D N-doped carbon nano-polyhedrons embedded with Co4N nanoparticles (denoted as 2D/3D Co4N-NC@CC) is designed as a sulfur host for RT Na-S battery. The complex structure of 2D/3D composite guarantees abundant adsorption and catalytic sites, accelerating electrons/mass transport abilities compared with single 2D or 3D structure, in which Co4N can effectively catalyze the conversion of NaPSs and inhibit “shuttling effect”. Consequently, the RT Na-S cell with 2D/3D Co4N-NC@CC cathode exhibits extra-high discharge capacity of 466 mAh g−1 at 3.0 C and an outstanding long-term cycling stability (592 mAh g−1 at 1.0 C after 1000 cycles). The hybrid 2D/3D Co4N-NC@CC with excellent electrochemical performance represents a potential candidate for developing advanced RT Na-S batteries and other energy storage systems.

Cobalt, nitrogen co-doped microporous carbon matrix derived from metal organic frameworks toward high specific capacity room temperature sodium sulfur batteries

Room-temperature sodium-sulfur (RT Na–S) batteries have been getting increasing attention in the field of energy storage system thanks to their advantages of high specific capacity, good safety, low cost and environmental friendliness. However, limited by the low conductivity, large volume change and complex reaction, the utilization rate of active sulfur is still unacceptable, which delays the practical application of RT Na–S battery. Herein, derived from CoZn-ZIFs, a cobalt, nitrogen co-doped microporous carbon matrix (Co,N-MPC) has been devised to exploit capacity of active sulfur as fully as possible. In the case of appropriate Co content, the affluent micropores limit the size of sulfur and inhibit the volume change. And the well-dispersed Co and N elements improve the adsorption of the matrix to sulfur species and promote their transformation process. Owing to their synergistic effect, the S@Co,N-MPC-10% electrode presents stable cycling (1134.63 mAh g−1 after 100 cycles at 0.2 C) and high rate capacity (835.01 mAh g−1 at 3.0 C). This work might provide beneficial insights to the development of efficient sulfur matrixes of RT Na–S batteries.

Understanding the Redox Mechanism of Sulfurized Poly(acrylonitrile) as Highly Rate and Cycle Stable Cathode Material for Sodium-Sulfur Batteries

Room temperature sodium-sulfur (RT Na-S) batteries are considered potential candidates for stationary power storage applications due to their low cost, broad active material availability and low toxicity. Challenges, such as high volume expansion of the S-cathode upon discharge, low electronic conductivity of S as active material and herewith limited rate capability as well as the shuttling of polysulfides (PSs) as intermediates often impede the cycle stability and practical application of Na-S batteries. Sulfurized poly(acrylonitrile) (SPAN) inherently inhibits the shuttling of PSs and shows compatibility with carbonate-based electrolytes, however, its exact redox mechanism remained unclear to date. Herein, we implement a commercially available and simple electrolyte into the Na-SPAN cell chemistry and demonstrate its high rate and cycle stability. Through the application of in situ techniques utilizing electronic impedance spectroscopy (EIS) and X-ray absorption spectroscopy (XAS) at different depths of charge and discharge, an insight into SPAN’s redox chemistry is obtained.