RESUMEN

The notorious polysulfide shuttling and uncontrollable Li-dendrite growth are the main obstacles to the marketization of Li-S batteries. Herein, a dual-functional material consisting of vacancy-rich quantum-sized Co nanodots anchored on a mesoporous carbon layer (v-Co/meso-C) is proposed. This material exposes more active sites to improve its reaction performance and simultaneously realizes excellent lithiophilicity and sulfiphilicity characteristics in Li-S electrochemistry. As Li metal deposition hosts, v-Co/meso-C shows small nucleation overpotential, low polarization, and ultra-long cycling stability in both half and symmetric cells, as confirmed by experimental studies. On the S cathode side, experimental and theoretical calculations demonstrate that v-Co/meso-C enhances the adsorption of polysulfides and boosts their catalytic conversion rate. This, in turn, suppresses the shuttle effect of polysulfides and improves sulfur utilization efficiency. Finally, a shuttle-free and dendrite-free v-Co/meso-C@Li//v-Co/meso-C@S full cell is fabricated, exhibiting excellent rate performance (739 mAh g-1 at 5.0 C) and good cyclability (capacity decay rate is 0.033% and 0.035% per cycle at 2.0 and 5.0 C, respectively). Even a pouch cell with high sulfur loading (5.5 mg cm-2) and lean electrolyte/sulfur (4.8 µL mg-1) can still work 50 cycles with 80% capacity retention rate. This study shows far-reaching implications in the design of dendrite-free, shuttle-free Li-S batteries.

RESUMEN

Sulfur undergoes various changes, including the formation of negative charge-bearing lithium polysulfides during the operation of Li-S batteries. Dissolution of some of the polysulfides in battery electrolytes is one of the reasons for the poor performance of Li-S batteries. The charge injection into the sulfur and polysulfides from the electrode is also a problem. To address these issues, a small-molecule additive, 3,6-di(pyridin-4-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione, was designed and synthesized with carbonyl oxygen atoms and two types of nitrogen. The pyridinic nitrogen increases the electronegativity of the carbonyl oxygen atoms. The pyridinic nitrogen, carbonyl oxygen, and lactam nitrogen provide multiple binding sites concurrently to the polysulfides, which increases the binding efficiency between the additive and polysulfides. A control molecule without the pyridine moiety displayed decreased binding to lithium polysulfides. Furthermore, the band edges of lithium polysulfide and 3,6-di(pyridin-4-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione are commensurate for efficient charge transfer between them, leading to the efficient electrocatalysis of lithium polysulfides. The cyclic voltammogram of the Li-S battery fabricated with 3,6-di(pyridin-4-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione exhibited sharp and well-defined peaks, confirming the formation of Li2Sy (where y varies between one and eight) from S8. These Li-S batteries showed a specific capacity of 950 mA h/g at 0.5 C, with a capacity retention of 70% at the 300th cycle. The pyridine-free control molecule, 3,6-diphenyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione, showed relatively poor performance in a Li-S battery.

RESUMEN

The metal-catalyzed sulfur reaction in lithium-sulfur (Li-S) batteries usually suffers from the strong binding of sulfur species to the catalyst surface, which destroys the electric double layer (EDL) region there. This causes rapid catalyst deactivation because it prevents the desorption of sulfur species and mass transport through the EDL is hindered. This work introduces a competitive adsorption factor (fsulfur) as a new indicator to quantify the competitive adsorption of sulfur species in the EDL and proposes an alloying method to change it by strengthening the p-d hybridization of alloying metals with electrolyte solvents. A cobalt-zinc alloy catalyst with a moderate fsulfur lowers the activation energy of the rate-limiting step of the conversion of lithium polysulfides to lithium sulfide, giving a platform capacity proportion that is 96% of the theoretical value and has a greatly improved anti-passivation ability, especially at high sulfur loadings and lean electrolyte conditions (a low E/S ratio of 5 µL mgS -1). A pouch cell using this approach has a high energy density of up to 464 Wh kg-1. Such a competitive adsorption indicator and alloying strategy offer a new guideline for catalyst design and a practical electrocatalysis solution for Li-S batteries.

RESUMEN

Despite the very high theoretical energy density, Li-S batteries still need to fundamentally overcome the sluggish redox kinetics of lithium polysulfides (LiPSs) and low sulfur utilization that limit the practical applications. Here, highly active and stable cathode, nitrogen-doped porous carbon nanotubes (NPCTs) decorated with NixCo1-xS2 nanocrystals are systematically synthesized as multi-functional electrocatalytic materials. The nitrogen-doped carbon matrix can contribute to the adsorption of LiPSs on heteroatom active sites with buffering space. Also, both experimental and computation-based theoretical analyses validate the electrocatalytic principles of co-operational facilitated redox reaction dominated by covalent-site-dependent mechanism; the favorable adsorption-interaction and electrocatalytic conversion of LiPSs take place subsequently by weakening sulfur-bond strength on the catalytic NiOh 2+-S-CoOh 2+ backbones via octahedral TM-S (TM = Ni, Co) covalency-relationship, demonstrating that fine tuning of CoOh 2+ sites by NiOh 2+ substitution effectively modulates the binding energies of LiPSs on the NixCo1-xS2@NPCTs surface. Noteworthy, the Ni0.261Co0.739S2@NPCTs catalyst shows great cyclic stability with a capacity of up to 511 mAh g-1 and only 0.055% decay per cycle at 5.0 C during 1000 cycles together with a high areal capacity of 2.20 mAh cm-2 under 4.61 mg cm-2 sulfur loading even after 200 cycles at 0.2 C. This strategy highlights a new perspective for achieving high-energy-density Li-S batteries.

RESUMEN

The application of Li-S batteries on large scale is held back by the sluggish sulfur kinetics and low synthesis efficiency of sulfur host. In addition, the preparation of catalysts that promote polysulfide redox kinetics is complex and time-consuming, reducing the cost of raw materials in Li-S. Here, a universal synthetic strategy for rapid fabrication of sulfur cathode and metal compounds nanocatalysts is reported based on microwave heating of graphene. Heat-sensitive materials can achieve rapid heating due to graphene reaching 500 ℃ within 4 s via microwave irradiation. The MoP-MoS2/rGO catalyst demonstrated in this work was synthesized within 60 s. When used for catalysts for Li-S batteries whose graphene/sulfur cathodes were also synthesized by microwave heating, enhanced catalytic effect for sulfur redox reaction was verified via experimental and DFT theoretical results. Benefiting from fast redox reaction (MoP), smooth Li+ diffusion pathways (MoS2), and large conductive network (rGO), the assembled Li-S battery with MoP-MoS2/rGO-Add@CS displays a remarkable initial specific capacity, stable lithium anode and good cycle stability (in pouch cells) using this two-pronged strategy. The work provides a practical strategy for advanced Li-S batteries toward a wide range of applications.

RESUMEN

The shuttle effect of soluble lithium polysulfides (LiPSs) poses a crucial challenge for commercializing lithium-sulfur batteries. The functionalization of the separator is an effective strategy for enhancing the cell lifespan through the capture and reuse of LiPSs. Herein, a novel In2O3 nanorod with an ultrathin carbon layer (In2O3@C) was coated on a polypropylene separator. The results demonstrate the adsorption and catalysis of In2O3 on polysulfides, effectively inhibiting the shuttle effect and improving the redox kinetics of LiPSs. Besides, the ultrathin carbon layer increases the reaction sites and accelerates the electrochemical reaction rate. The cell with the In2O3@C interlayer displays excellent reversibility and stability with a 0.029% capacity decay each cycle in 2000 cycles at 2C. In addition, the In2O3@C interlayer significantly improves the cell performance under high current (888.2 mA h g-1 at 2C and room temperature) and low temperature (1007.8 mA h g-1 at 0.1C and -20 °C) conditions.

RESUMEN

As a very prospective solid-state electrolyte, Li10GeP2S12 (LGPS) exhibits high ionic conductivity comparable to liquid electrolytes. However, severe self-decomposition and Li dendrite propagation of LGPS will be triggered due to the thermodynamic incompatibility with Li metal anode. Herein, by adopting a facile chemical vapor deposition method, an artificial solid electrolyte interphase composed of Li2S is proposed as a single ionic conductor to promote the interface stability of LGPS toward Li. The good electronic insulation coupled with ionic conduction property of Li2S effectively blocks electron transfer from Li to LGPS while enabling smooth passage of Li ions. Meanwhile, the generated Li2S layer remains good interface compatibility with LGPS, which is verified by the stable Li-plating/stripping operation for over 500 h at 0.15 mA cm-2. Consequently, the all-solid-state Li-S batteries (ASSLSBs) with a Li2S layer demonstrate superb capacity retention of 90.8% at 0.2 mA cm-2 after 100 cycles. Even at the harsh condition of 90 °C, the cell can deliver a high reversible capacity of 1318.8 mAh g-1 with decent capacity retention of 88.6% after 100 cycles. This approach offers a new insight for interface modification between LGPS and Li and the realization of ASSLSBs with stable cycle life.

RESUMEN

Given that both elemental sulfur (S8) and lithium sulfide (Li2S) exhibit insulating properties, the involvement of conductive host materials becomes crucial for facilitating charge transfer in sulfur cathodes within lithium-sulfur (Li-S) batteries. Furthermore, there has been a recent surge in the exploration of host materials for sulfur cathodes to address the "polysulfide shuttle" effect. This effect arises from the formation of polysulfide species during the charge-discharge cycles of the Li-S batteries and can be mitigated through physical or chemical interactions with specific materials. To qualitatively and accurately assess the interactions between polysulfides and the potential host materials, this study utilized a well-established high-performance liquid chromatography method for polysulfide analysis. The objective was to monitor the changes in polysulfide solutions after contact with 44 different carbon and inorganic materials. Based on both qualitative and quantitative chromatographic results, it was determined that 20 out of the 44 materials exhibit significant interactions with polysulfides. The primary form of interaction observed is the irreversible disproportionation reaction with elemental sulfur being one of the resulting products.

RESUMEN

The shuttle effect of soluble lithium polysulfides (LiPSs) is primarily responsible for the unstable performance of lithium-sulfur (Li-S) batteries, which has severely impeded their continued development. In order to solve this problem, a special strategy is proposed. Specifically, ultra-thin NiCo based layered double hydroxides (named LDH or NiCo-LDH) nanosheets are implanted into a pre-designed 3D interconnected carbon networks (SPC) to obtain porous composite materials (named SPC-LDH).During the operation of the battery, the 3D interconnected porous carbon mesh was the first to rapidly adsorb LiPSs, and then the LDH on the surface of the carbon mesh was used to realize the catalytic conversion of LiPSs. This facilitates the electrochemical conversion reaction between S substances while addressing the "shuttle effect". As a result, the battery maintains a discharge capacity of 1401.9, 1114.3, 975.5, 880.7, 760.4 and 679.6 mAh g-1 at the current densities of 0.1, 0.2, 0.5, 1, 2 and 3C, respectively. After 200 cycles at 2C, the battery's capacity stays at 732.9 mAh g-1, meaning that the average rate of capacity decay is only 0.007 % per cycle. Moreover, in-situ XRD demonstrates the critical function of PP/SPC-LDH separators in inhibiting LiPSs and encouraging Li2S transformation. The strong affinity of SPC-LDH for Li2S6 is also confirmed by density functional theory (DFT) calculation, offering more theoretical support for the synergistic adsorption process. This work offers a compelling method to develop modified separator materials that can counteract the "shuttle effect" in Li-S batteries.

RESUMEN

The practical application of Li-S batteries (LSBs) has long been impeded by the inefficient utilization of sulfur and slow kinetics. Utilizing conductive carbonaceous frameworks as a host scaffold presents an efficient and cost-effective approach to enhance sulfur utilization for redox reactions in LSBs. However, the interaction of pure carbon materials with lithium polysulfide intermediates (LiPSs) is limited to weak van der Waals forces. Hence, the development of an economical method for synthesizing heteroatom-doped carbon materials for sulfur fixation is of paramount importance. In this study, we introduce a hierarchical porous nitrogen-doped carbon sponge (NPCS) with an exceptionally high BET surface area of 3182.2 m2 g-1, achieved through a facile template-assisted polymerization method. The incorporation of inorganic salts, free radical polymerization, and deuteric freeze-drying techniques facilitates the formation of hierarchical pores within the NPCS. After sulfur fixation, the resulting S/NPCS electrode demonstrates remarkable electrochemical performance in LSBs. Specifically, it achieves an 80% sulfur utilization rate, maintains a high reversible specific capacity of 400 mA h g-1 even after 600 cycles at a demanding current density of 5.0 A g-1, and exhibits superior rate capability. It is believed that this work will inspire the rational design of cost-effective carbon-based electrodes for high-performance LSBs.

RESUMEN

The shuttle effect, sluggish conversion kinetics, and uncontrollable lithium dendrites seriously hinder the practical application of lithium-sulfur (Li-S) batteries. Among many modified materials, covalent organic frameworks (COFs) stand out for their excellent ability to inhibit the shuttle effect, while their role in promoting lithium nucleation and catalyzing the conversion of sulfur species has been largely ignored. In this study, an integrated COF separator (TpPa@2400) is developed as a rapid lithium nucleator and sulfur species catalyst in fast-charging Li-S batteries. According to the adsorption energy and Bader charge results, Li atoms preferentially adsorb onto the surface of the TpPa@2400 separator, and the larger Bader charge value (0.52 |e|) of the TpPa@2400 separator also signifies faster lithium transport, promoting the nucleation of Li ions. Furthermore, density functional theory (DFT) theoretically demonstrates that the TpPa@2400 separator exhibits lower free energy for sulfur species interconversion. As a result, the TpPa@2400 separator enables the Li-Li symmetric cell with an extended cycle life of 6000 h at a current density/capacity of 10 mA cm-2/10 mAh cm-2. The Li-S battery assembled using the TpPa@2400 separator delivers a high capacity of 1636.4 mAh/g at 0.1C and a rapid sulfur species conversion capacity of 513.8 mAh/g at 2C.

RESUMEN

Lithium-sulfur batteries offer the potential for significantly higher energy density and cost-effectiveness. However, their progress has been hindered by challenges such as the "shuttle effect" caused by lithium polysulfides and the volume expansion of sulfur during the lithiation process. These limitations have impeded the widespread adoption of lithium-sulfur batteries in various applications. It is urgent to explore the high-performance sulfur host to improve the electrochemical performance of the sulfur electrode. Herein, bimetallic NiFe hydroxide (NiFe-LDH)-modified carbon nanotubes (CNTs) are prepared as the sulfur host materials (NiFe-CNT@S) for loading of sulfur. On the one hand, the crosslinked CNTs can increase the electron conductivity of the sulfur host as well as disperse NiFe-LDHs nanosheets. On the other hand, NiFe-LDHs command the capability of strongly adsorbing lithium polysulfides and also accelerate their conversion, which effectively suppresses the shuttle effect problem in lithium polysulfides. Hence, the electrochemical properties of NiFe-CNT@S exhibit significant enhancements when compared with those of the sulfur-supported pure NiFe-LDHs (NiFe-LDH@S). The initial capacity of NiFe-CNT@S is reported to be 1010 mAh g-1. This value represents the maximum amount of charge that the material can store per gram when it is first synthesized or used in a battery. After undergoing 500 cycles at a rate of 2 C (1 C = 1675 mA g-1), the NiFe-CNT@S composite demonstrates a sustained capacity of 876 mAh g-1. Capacity retention is a measure of how well a battery or electrode material can maintain its capacity over repeated charge-discharge cycles, and a higher retention percentage indicates better durability and stability of the material.

RESUMEN

Li-S batteries possess high energy density and have been one of the most promising energy storage systems. For sulfur cathodes, the electrochemical performance is still seriously hindered by the polysulfide shuttling and sluggish conversion kinetics. It has been demonstrated to be one effective strategy to address the above issues via designing electrocatalysts with robust affinity and catalytic capacity towards polysulfides. However, it is still a great challenge to rapidly and economically discover high-performance electrocatalysts. Herein, using density functional theory calculation, we studied the chemisorption-catalysis behavior of sulfur species on a series of electrocatalysts (MCo2 X4 , M=Co, Zn, Cu, Ni, Fe, and Mn, X=O, S, and Se) to assess the effect of the anions and cations co-regulation on their electronic structure, chemisorption behavior, and catalytic property. FeCo2 Se4 and CuCo2 Se4 combined appropriate chemisorption with superior electronic conductivity and sulfur reduction catalytic capacity have been predicted as novel electrocatalysts for high-performance Li-S batteries. This study gives theoretical guidance for rapid discovery of high-efficient electrocatalyst to boost the electrochemical performance of sulfur cathodes.

RESUMEN

The commercialization of lithium-sulfur (Li-S) batteries is challenging, owing to factors like the poor conductivity of S, the 'shuttle effect', and the slow reaction kinetics. To address these challenges, MoP quantum dots were decorated on hollow carbon spheres (MoPQDs/C) in this study and used as an efficient lithium polysulfides (LiPSs) adsorbents and catalysts. In this approach polysulfides are effectively trapped through strong chemisorption and physical adsorption while simultaneously facilitating LiPSs conversion by enhancing the reaction kinetics. MXene serves as a flexible physical barrier (MoPQDs/C@MXene), further enhancing the confinement of LiPSs. Moreover, both materials are conductive, significantly facilitating electron and charge transfer. Additionally, the flexible MoPQDs/C@MXene-S electrode offers a large specific surface area for sulfur loading and withstand volume expansion during electrochemical processes. As a result, the MoPQDs/C@MXene-S electrode exhibits excellent long-term cyclability and maintains a robust specific capacity of 992 mA h g-1 even after 800cycles at a rate of 1.0C (1C = 1675 mA g-1), with a minimal capacity decay rate of 0.034 % per cycle. This work proposes an efficient strategy to fabricate highly efficient electrocatalysts for advanced Li-S batteries.

RESUMEN

To improve the electrochemical performance of Li-S batteries, a cathodic material (rGO150/S/CF-75) was fabricated for Li-S batteries by adopting a melt-flow method to load sulfur on biomass-derived carbon fibers, then the reduced graphene oxide was electrochemically covered on the outside surface of the sulfur. The coverage of reduced graphite oxide layers endows the performance of S/CF-75 multiple improvements. The specific capacity of rGO150/S/CF-75 cathode delivers a specific capacity of 1451.4 mAh g-1 at 0.1 A g-1. The specific capacity of rGO150/S/CF-75 cathode can still maintain 537.3 mAh g-1 after 1000 cycles at 5 A g-1 (109 % capacity retention). The excellent performance of rGO150/S/CF-75 cathode is benefit from not only the conductive paths of reduced graphene oxide layers and protective function of reduced graphene oxide layers inhibiting that the soluble sulfur diffuse into bulk electrolyte, but also the redistribution of sulfur on conductive carbon components during the cycling process.

Asunto(s)

RESUMEN

Lithium-sulfur (Li-S) batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost. Nevertheless, the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value. Many methods were proposed for inhibiting the shuttle effect of polysulfide, improving corresponding redox kinetics and enhancing the integral performance of Li-S batteries. Here, we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li-S batteries. First, the electrochemical principles/mechanism and origin of the shuttle effect are described in detail. Moreover, the efficient strategies, including boosting the sulfur conversion rate of sulfur, confining sulfur or lithium polysulfides (LPS) within cathode host, confining LPS in the shield layer, and preventing LPS from contacting the anode, will be discussed to suppress the shuttle effect. Then, recent advances in inhibition of shuttle effect in cathode, electrolyte, separator, and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li-S batteries. Finally, we present prospects for inhibition of the LPS shuttle and potential development directions in Li-S batteries.

RESUMEN

In this manuscript, nickel/cobalt bimetallic nanocrystals confining into three-dimensional interpenetrating dual-carbon conductive structure (NiCo@C/CNTs) were successfully manufactured by annealing its core-shell structure (Ni-ZIF-67@ZIF-8) precursor under the high temperature. The results presented that the bimetallic nickel and cobalt nanocrystals with superior catalytic activity could quickly convert solid Li2S/Li2S2into soluble LiPSs and effectively decrease the energy barrier. While the hierarchical CNT-porous carbon dual frameworks can provide quick electron/ion transport because of their large specific surface area and the exposure of enough active sites. When used as the separator modifier for lithium sulfur batteries, the battery properties were significantly improved with high specific capacity, outstanding rate capability, and long-term cycle stability. Specifically, its initial specific capacity can achieve to 1038.51 mAh g-1 at 0.5C. At the high rate of 3C, it still delivers satisfactory discharge capacity of 555 mAhg-1 and the capacity decay rate is only 0.065% per cycle after 1000 cycles at 1C. Furthermore, even exposed to heavy sulfur loading (3.61 mg/cm2), they still maintain promising cycle stability. Therefore, such kinds of MOFs derivative with powerful chemical immobilization and catalytic conversion for polysulfides provides a novel guidance for the modification separator and the potential application in the field of high-performance Li-S batteries.

RESUMEN

The design and construction of three-dimensional covalent organic frameworks (3D COF) remains a major challenge, and it is necessary to explore new strategies to synthesize 3D COF with ideal structure. Here, we utilize two-dimensional covalent organic framework (2D COF) with allyl side chain to achieve interlayer crosslinking through olefin metathesis reaction, thereby constructing a 3D COF with cage-like structures. This new material named CAGE-COF has larger specific surface area and more open pore structure than the original 2D COF. The cathode material with CAGE-COF retained 78.7% of its initial capacity after 500 cycles, and the fading rate is 0.04% each cycle.

Asunto(s)

RESUMEN

The practical application of lithium-sulfur batteries (LSBs) is still hindered by several technical issues, including severe polysulfide shuttling and sluggish redox kinetics, which reduces the sulfur utilization and further results in low energy density. Herein, amorphous-crystalline heterostructured MnO2 (ACM) prepared through a simple calcination process was employed as the functional interlayer to play a double role as effective trapper and multifunctional electrocatalyst for LSBs. ACM not only combines the strong sulfur chemisorption of the amorphous MnO2 (AM) and fast Li+ transportation of the crystalline MnO2(CM) but also accelerates the interface charge transfer at the amorphous/crystalline interfaces. The LSBs with such unique interlayer exhibited an excellent rate performance of 1155.5 mAh·g-1 at 0.2 C and 692.9 mAh·g-1 at 3 C and a low decay rate of 0.071% per cycle over 500 cycles at 0.5 C. Even for a high sulfur loading of 5 mg·cm-2 at 0.1 C, a high capacity retention of 92.3% could also be achieved after 100 cycles. The concept of amorphous-crystalline heterostructures prepared by crystallization regulation might also be used for other electronic devices and catalyst designs.

RESUMEN

Solid-state lithium metal batteries offer superior energy density, longer lifespan, and enhanced safety compared to traditional liquid-electrolyte batteries. Their development has the potential to revolutionize battery technology, including the creation of electric vehicles with extended ranges and smaller more efficient portable devices. The employment of metallic lithium as the negative electrode allows the use of Li-free positive electrode materials, expanding the range of cathode choices and increasing the diversity of solid-state battery design options. In this review, we present recent developments in the configuration of solid-state lithium batteries with conversion-type cathodes, which cannot be paired with conventional graphite or advanced silicon anodes due to the lack of active lithium. Recent advancements in electrode and cell configuration have resulted in significant improvements in solid-state batteries with chalcogen, chalcogenide, and halide cathodes, including improved energy density, better rate capability, longer cycle life, and other notable benefits. To fully leverage the benefits of lithium metal anodes in solid-state batteries, high-capacity conversion-type cathodes are necessary. While challenges remain in optimizing the interface between solid-state electrolytes and conversion-type cathodes, this area of research presents significant opportunities for the development of improved battery systems and will require continued efforts to overcome these challenges.