Search Results (93)

Films of functionalised multiwalled carbon nanotubes (MWCNTs) were fabricated as interlayers (interfacial layers between the cathode and separator) in a lithium–sulfur battery (LSB). Phenylsulfonate functionalisation of commercial MWCNTs was achieved via diazotisation to attach lithium phenylsulfonate groups and was characterised by IR and XPS spectroscopies. SEM-EDX showed sulfur and oxygen colocations due to the sulfonate groups on the interlayer surface. However, CHNS elemental microstudies showed a low degree of functionalisation. Without an interlayer, the LSB produced stable cycling at a capacity of 600 mA h g⁻¹_sulfur at 0.05 C for 40 cycles. Using an unfunctionalised interlayer as a control gave a capacity of 1400 mA h g⁻¹_sulfur for the first cycle but rapidly decayed to the same 600 mA h g⁻¹_sulfur at the 40th cycle at 0.05 C, suggesting a high degree of polysulfide shuttling. Adding a lithium phenylsulfonated interlayer gave an initial capacity increase to 1100 mA h g⁻¹_sulfur that lowered to 800 mA h g⁻¹_sulfur at 0.05 C by the 40th cycle, showing an increase in charge storage (33%) relative to the other cells. This performance increase has been attributed to lessened polysulfide shuttling due to repulsion by the phenylsulfonate groups, increased conductivity at the separator-cathode interface and an increase in surface area. Full article

Lithium–sulfur (Li-S) batteries are hindered by the sluggish electrochemical kinetics and poor reversibility of lithium polysulfides (LiPSs), which limits their practical energy density and cycle life. In order to address this issue, a novel Ni₃N/Nb₄N₅ heterostructure was synthesized via electrospinning and nitridation as a functional coating for polypropylene (PP) separators. Adsorption experiments were conducted in order to ascertain the heterostructure’s superior affinity for LiPSs, thereby effectively mitigating their shuttling. Studies of Li₂S nucleation demonstrated the catalytic role of the substance in accelerating the deposition kinetics of Li₂S. Consequently, Li-S cells that employed the Ni₃N/Nb₄N₅-modified separator were found to achieve significantly enhanced electrochemical performance, with the cells delivering an initial discharge capacity of 1294.4 mAh g⁻¹ at 0.2 C. The results demonstrate that, after 150 cycles, the cells retained a discharge capacity of 796.2 mAh g⁻¹, corresponding to a low capacity decay rate of only 0.25% per cycle. In addition, the rate capability of the cells was found to be improved in comparison to control cells with NiNb₂O₆-modified or pristine separators. Full article

Exploring advanced sulfur cathode materials is important for the development of lithium-sulfur batteries (LSBs), but they still present challenges. Herein, zinc oxide dots-modified vanadium nitride flower-like heterojunctions (Zn-QDs-VN) as sulfur hosts are prepared by a phase separation strategy. Characterizations confirm that the flower structure with high specific surface area and pores improves active site exposure and electron/mass transfer. In situ phase separation enriches the Zn-QDs-VN interface, addressing the issues of uneven distribution and interface reduction of Zn-QDs-VN. Further theoretical computations reveal that ZnO-QDs-VN with optimized intermediate spin states can constitute a stable LiS* bond sequence, which can conspicuously facilitate the adsorption and conversion of LiPSs and reduce the battery reaction energy barrier. Therefore, the ZnO-QDs-VN@S cathode shows a high initial specific capacity of 1109.6 mAh g⁻¹ at 1.0 C and long cycle stability (maintaining 984.2 mAh g⁻¹ after 500 cycles). Under high S loading (8.5 mg cm⁻²) and lean electrolyte conditions (E/S = 6.5 μL mg⁻¹), it also exhibits a high initial area capacity (10.26 mAh cm⁻²) at 0.2 C. The interfacial synergistic effect accelerates the adsorption and conversion of LiPSs and reduces the energy barriers in cell reactions. The study provides a new method for designing heterojunctions to achieve high-performance LSBs. Full article

The comprehensive recycling of aluminum electrolysis cell waste barrier material is urgent. This study focuses on the sulfuric acid leaching of waste barrier material, systematically examining the effects of factors such as reaction temperature, liquid-to-solid ratio, sulfuric acid concentration, and reaction time on the leaching of elements like lithium, aluminum, sodium, and silicon. The experimental results show that under the conditions of 0.9 mol/L sulfuric acid concentration, a liquid-to-solid ratio of 20:1, a reaction temperature of 90 °C, and a reaction time of 1.5 h, the leaching rates were 84.5% for lithium, 85.6% for aluminum, 98.5% for sodium, and 4.8% for silicon. The sulfuric acid leaching process of the waste barrier material follows a shrinking core model and is controlled by internal diffusion. The apparent activation energies for the leaching reactions of lithium, aluminum, and sodium were 4.29 kJ/mol, 8.99 kJ/mol, and 9.11 kJ/mol, respectively. The selective leaching of lithium, sodium, and aluminum from silicon was successfully achieved in the sulfuric acid leaching of the waste barrier material. Full article

Although silicon-based anodes have been identified as a potential alternative to conventional graphite anodes, the huge volume change (approximately 300%) that occurs in silicon while cycling still impedes this system from practical applications. In the case of silicon-suboxide (SiO_x)-based anode materials, both Li₂O and LiSiO₄ are formed during the initial lithiation processes and act as a natural volume buffer matrix to accommodate volume changes and the formation of a stable SEI layer, which improves the cyclability and capacity retention. In this study, a series of SiO_x/Si/C-based electrodes composed of different amorphous SiO_x, Si, and graphitic carbon contents were prepared. Among the various investigated compositions, the electrode with a ratio of SiO_x-Si-C equal to 70:12.5:12.5 was found to be optimal in terms of discharge capacity. This promising electrode was pre-lithiated prior to cycling. Finally, 2032-type lithium–sulfur (Li-S) coin cells composed of a S-C/SiO_x-Si-C (pre-lithiated) configuration were assembled and their cycling performances are reported. Full article

Laser conversion of commercial polymers to laser-induced graphene (LIG) using inexpensive and accessible CO₂ lasers has enabled the rapid prototyping of promising electronic and electrochemical devices. Frequently used to pattern interdigitated supercapacitors, few approaches have been developed to pattern batteries—in particular, full cells. Herein, we report an LIG-based approach to a planar, interdigitated Li-S battery. We show that sulfur can be deposited by selective nucleation and growth on the LIG cathode fingers in a supersaturated sulfur solution. Melt imbibition then leads to loadings as high as 3.9 mg/cm² and 75 wt% sulfur. Lithium metal anodes are electrodeposited onto the LIG anode fingers by a silver-seeded, pulse-reverse-pulse method that enables loadings up to 10.5 mAh/cm² to be deposited without short-circuiting the interdigitated structure. The resulting binder/separator-free flexible battery achieves a capacity of over 1 mAh/cm² and an energy density of 200 mWh/cm³. Unfortunately, due to the use of near stoichiometric lithium, the cycle-life is sensitive to lithium degradation. While future work will be necessary to make this a practical, flexible battery, the interdigitated structure is well-suited to future operando and ex situ studies of Li-S and related battery chemistries. Full article

Lithium–sulfur (Li–S) batteries have emerged as a promising candidate for next-generation high-energy rechargeable lithium batteries, but their practical application is impeded by the sluggish redox kinetics and low sulfur loading. Here, we report the in situ growth of δ-MnO₂ nanosheets onto hierarchical porous carbon microspheres (HPCs) to form an HPCs/S@MnO₂ composite for advanced lithium–sulfur batteries. The delicately designed hybrid architecture can effectively confine LiPSs and obtain high sulfur loading up to 10 mg cm⁻², in which the inner carbon microspheres with a large pore volume and large specific surface area can encapsulate high sulfur content, and the outer MnO₂ nanosheets, as a catalytic layer, can improve the conversion reaction of LiPSs and suppress the shuttle effect. The thick HPCs/S@MnO₂ electrode with 7 mg cm⁻² sulfur loading delivers an areal capacity of 4.0 mAh cm⁻² at 0.1 C and provides stable cycling stability with a low-capacity decay rate of 0.063 % per cycle after 200 cycles at 0.1 C. Furthermore, a Li–S pouch cell with a capacity of 2.5 A h is fabricated and demonstrates high cycling stability. This work offers a feasible method to build advanced sulfur electrodes with high areal loading and sheds light on their commercial application in high-performance Li–S batteries. Full article

Li–S batteries are promising large-scale energy storage systems but currently suffer from performance issues; a major reason is the dissolution of polysulfides in electrolytes. To this end, we report a high-energy-density Lithium–Sulfur (Li–S) battery that combines a catholyte and a sulfur-free carbon nanofiber (CNF) cathode. The cathode was synthesized by carbonizing binder-free polyacrylonitrile (PAN) nanofibers, affording a high surface area. In the catholyte, added polysulfides acted as both conductive Li salts and active materials. Investigating the electrochemical performance of this concept in both Swagelok- and pouch-type cells afforded energy densities exceeding 3 mAh cm⁻² at a discharge rate of 0.1 C. This combination could also be utilized in high-capacity pouch cells with capacities of up to 250 mAh g⁻¹. Both cell types exhibited good cycle performance. Adding LiNO₃ to the electrolyte suppressed the redox shuttle reactions. Moreover, the cathode being binder-free increased the energy density and simplified cathode fabrication. Characterizing the cathode before and after cycling revealed that deposition was reversible, and that cell reactions at least partially formed sulfur as the end product, resulting in high sulfur amounts in the cell. We expect our concept to greatly aid in the development of practically applicable Li–S cells. Full article

As a better alternative to lithium-ion batteries (LIBs), lithium–sulfur batteries (LSBs) stand out because of their multi-electron redox reactions and high theoretical specific capacity (1675 mA h g⁻¹). However, the long-term stability of LSBs and their commercialization are significantly compromised by the inherently irreversible transition of soluble lithium polysulfides (LiPS) into solid short-chain S species (Li₂S₂ and Li₂S) and the resulting substantial density change in S. To address these issues, we used activated carbon cloth (ACC) coated with Ni₁₂P₅ as a porous, conductive, and scalable sulfur host material for LSBs. ACC has the benefit of high electrical conductivity, high surface area, and a three-dimensional (3D) porous architecture, allowing for ion transport channels and void spaces for the volume expansion of S upon lithiation. Ni₁₂P₅ accelerates the breakdown of Li₂S to increase the efficiency of active materials and trap soluble polysulfides. The highly effective Ni₁₂P₅ electrocatalyst supported on ACC drastically reduced the severity of the LiPS shuttle, affected the abundance of adsorption–diffusion–conversion interfaces, and demonstrated outstanding performance. Our cells achieved near theoretical capacity (>1611 mA h g⁻¹) during initial cycling and superior capacity retention (87%) for >250 cycles following stabilization with a 0.05% decay rate per cycle at 0.2 C. Full article

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). Full article

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/g_S 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/g_S. Full article

Li–S batteries are positioned as a strong alternative for efficient energy storage due to their high theoretical energy density and their theoretical specific capacity (1675 mA h g⁻¹) compared to current Li-ion batteries; however, their commercialization is affected by the rapid decay of the specific capacity as a consequence of the different species of lithium polysulfides that are generated during the charge–discharge processes. The use of nitrogen-doped mesoporous carbon materials has been shown to have the ability to confer electronic conductivity to sulfur and retain the lithium polysulfide species. However, there are not enough studies to help understand how the type of nitrogen precursor influences the development of specific nitrogen functionalities to favor the retention of lithium polysulfide species. This work seeks to determine the effect of the use of different nitrogen precursors on the structural changes of the mesoporous carbon materials prepared, and thus evaluate the electrochemical behavior of Li–S cells correlating the type of nitrogen functionality generated when the precursor is variated with the charge/discharge capacity developed during the cell operation. For this study, different carbon materials were prepared by the variation of the nitrogen source (melamine, ethylenediamine, and hexadecylamine) to obtain a N-doped mesoporous carbon with different distributions of nitrogen functionalities in its structure. The use of the primary amine ethylenediamine as a nitrogen precursor in the formation of structured carbon materials favored elemental sulfur infiltration into its pores, resulting in the maximum sulfur content within the pores and interacting with the carbonaceous matrix (78.8 wt.%). The carbon material prepared with this precursor resulted in a higher content of N-pyridinic functionality, which, combined with the high content of N-pyrrolic, resulted in the highest specific discharge capacity at 0.1 C after 100 cycles when compared to cells assembled with materials derived from the use of melamine and hexadecylamine precursors. The cell assembled with the electrode formed from ethylenediamine as a nitrogen precursor presented an initial discharge capacity of 918 mA h g⁻¹ with a Coulombic efficiency of ~83.4% at 0.1 C after 100 cycles. Full article

Lithium–sulfur batteries suffer from a reduced cycle life and diminished coulombic efficiency, which is attributed to the polysulfide shuttle effect. We herein present a process for the fabrication of lithium–sulfur battery cathode material via the recrystallization of dissolved sulfur inside self-assembled carbon nanospheres synthesized through the carbonization of d-glucose. Trapping sulfur in the carbonaceous matrix lessens the rapid dissolution of polysulfides and minimizes the loss of active sulfur, thus extending the cycling stability of these batteries. The carbon–sulfur composite material was characterized via X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Electrochemical analysis of the material and its functionality as an electrode for lithium–sulfur battery systems was evaluated in a coin cell format using impedance spectroscopy and a life cycle study. The as-prepared cathode has shown remarkable electrochemical performance with a specific capacity of 781 mA/g at 0.1 C after 500 charge/discharge cycles and 83.4% capacity retention. Full article

Lithium–sulfur (Li-S) batteries have received much attention due to their high energy density and low price. In recent years, alleviating the volume expansion and suppressing the shuttle effect during the charge and discharge processes of Li-S batteries have been widely addressed. However, the slow conversion kinetics from polysulfide (LiPSs) to Li₂S₂/Li₂S still limits the application of Li-S batteries. Therefore, we designed a ZIF-67 grown on cellulose (named ZIF-67@CL) as an electrocatalyst to improve the interconversion kinetics from LiPSs to Li₂S₂/Li₂S for Li-S batteries. Based on the results of adsorption experiments of LiPSs, ZIF-67@CL and CL hosts were immersed in Li₂S₄ solution to adsorb LiPSs, and the UV-Vis test was conducted on the supernatant after adsorption. The results showed that the ZIF-67@CL had a stronger adsorption for LiPSs compared with the cellulose (CL). Furthermore, in the Li₂S nucleation tests, the fabricated cells were galvanostatically discharged to 2.06 V at 0.112 mA and then potentiostatically discharged at 2.05 V. Based on the results of Li₂S nucleation tests, the catalytic effect of ZIF-67 was further verified. As a result, the sulfur cathode used a ZIF-67 catalyst (named S/ZIF-67@CL) and delivered an initial capacity of 1346 mAh g⁻¹ at a current density of 0.2 C. Even at a high current density of 2 C, it exhibited a high-capacity performance of 1087 mAh g⁻¹ on the first cycle and maintained a capacity output of 462 mAh g⁻¹ after 150 cycles, with a Coulombic efficiency of over 99.82%. Full article

The implementation of a functional separator represents a highly encouraging approach to mitigating polysulfide shuttling in lithium–sulfur (Li–S). In this study, a two-dimensional (2D) 1,3,5-triformylphloroglucinol (Tp)-p-phenylenediamine (Pa) covalent organic framework/reduced graphene oxide (rGO) functional layer was introduced to enhance the performance of the commercial separator in Li–S batteries. The resulting 2D TpPa@rGO modified separators exhibit significantly improved electronic and ionic conductivity when compared to the unmodified separator, effectively mitigating lithium polysulfide shuttling and enhancing sulfur cathode utilization. It is indicated that a heterostructured composite of a nitrogen-group-containing COF and an electronic conductive addictive is an effective modification to the separator. Consequently, the modified cell demonstrated a minimal degradation rate of only 0.12% per cycle over 350 cycles at 0.5 C. Full article