Li-Se Batteries Research Articles

A Piezocatalysis Strategy to Enable Efficient Redox in Solid-State Battery.

Piezocatalysis is considered to be a favorable catalytic technology by utilizing external mechanical stimulation to promote the specific redox reactions. The application of piezocatalysis in batteries is promising but faces formidable challenges. Herein, the operation principles of piezocatalysis were successfully demonstrated by constructing a solid-state Li-Se (S) battery model with interfacial stress accumulation. Lead zirconate titanate with an ultra-high piezoelectric coefficient was applied as the piezoelectric catalyst. The uniformity of the dipole orientation in materials was essential for achieving piezocatalysis in batteries. The accumulated high-stress converts to piezopotential for catalyzing most reaction processes in batteries, while the rapid stress change prevents the internal charge reorganization, ensuring continuous efficient catalysis. The internal stress change alters the internal polarisation strength, driving excess screening charge to participate in the electrochemical reaction. Under piezocatalysis, solid-state Li-Se batteries exhibited a initial discharge capacity of 670.9 mAh g-1 (99.4% of the theoretical value) at 0.1C, and Li-S batteries showed a capacity of 1463 mAh g-1 at 0.2C, which was still maintained up to 1084 mAh g-1 at an elevated rate of 0.5C. This piezocatalysis strategy provides a strong theoretical basis and design specification for enhancing Li-Se (S) cell reaction kinetics.

Molten salt-assisted microporous biochar derived from poplar sawdust as an efficient cathode matrix for Li-Se battery applications

This study focuses on the employment of molten salts (ZnCl2-KCl-NaCl and K2CO3-Na2CO3-Li2CO3) as alternative activating agents to prepare porous biochars, which serve as efficient cathode matrices for Li-Se battery applications. Poplar sawdust was employed as the biomass feedstock, mixed with molten salts in a 1:5 mass ratio, and then pyrolyzed at a low temperature of 500 ℃ to obtain PB-Cl and PB-Carb, respectively. The obtained porous biochar samples were investigated, and processed for selenium (Se) loading using the melt-diffusion technique, resulting in composites named Se@PB-Cl and Se@PB-Carb, respectively. The composite Se@PB-Cl, with a BET surface area of 787.11 m2 g−1 and a t-plot micropores area of 691.65 m2 g−1, displayed a Se loading of 41.86 % and exhibited enhanced electrochemical performance. At 0.5 C, Se@PB-Cl after 100 cycles delivered a specific capacity of 617.03 mAh g−1. After 500 cycles, at 1 C a specific capacity of 505.9 mAh g−1 was observed. Moreover, the specific capacity of Se@PB-Carb was found to be 339.74 mAh g−1 at 0.5 C after 100 cycles, and 235.97 mAh g−1 at 1 C after 500 cycles. These findings highlight the potential of molten salt-assisted porous biochar obtained from poplar sawdust, as a cost-effective precursor for selenium-based cathodes.

High‐Capacity, Long‐Life All‐Solid‐State Lithium–Selenium Batteries Enabled by Lithium Iodide Active Additive

AbstractSelenium (Se) shows promise as a cathode candidate for all‐solid‐state lithium (Li) batteries due to its impressive theoretical volumetric energy density, much higher electronic conductivity, and improved safety in comparison to those for sulfur (S). An active cathode additive, lithium iodide (LiI) is demonstrated, to address the major challenge for all‐solid‐state Li–Se batteries, namely the sluggish redox kinetics resulting from the huge solid‐state conversion barrier. The LiI additive enhances Li+ transport and provides catalytic sites for Se cathode, thus endowing the batteries with accelerated reaction kinetics and extra capacity. DFT calculation and experimental analysis clearly reveal that LiI additive efficiently accelerates the conversion between polyselenide intermediates and Li2Se. With the above advantages, the battery with LiI using Li6PS5Br electrolyte gives an outstanding capacity of 862 mAh gSe−1 beyond the theoretical specific capacity of Se and a superlong life over 1800 cycles at 1C under room temperature. This work offers a simple strategy to facilitate the kinetics of all‐solid‐state Se cathodes and paves the way for the practicality of high‐capacity and long‐life all‐solid‐state Li–Se batteries.

Upcycling Plastic Waste into Porous Activated Carbon As Cathode Material for Lithium-Selenium Batteries

Selenium (Se) has a high specific capacity, rendering it a promising cathode material for rechargeable lithium (Li) batteries. Yet, challenges arise due to irreversible reactions and the shuttle effect in contact with electrolytes. This study addresses these issues by confining Se within a microporous carbon derived from non-recyclable plastic waste through a two-step carbonization/activation process. The resulting plastic waste-derived carbon (PWC) serves as a host for Se, forming cathode composites through a melt diffusion process. The cathode electrode was fabricated using a slurry casting method, comprising PWC/Se composite, carbon black, and sodium alginate (8:1:1 mass ratio). The evolution of the porous structure in PWC and its impact on the electrochemical performance of PWC/Se electrode were investigated for different activation temperatures (500, 600, 700, and 800 °C). The study revealed that the structure of PWC activated below 800 °C consists of mainly micropores. Moreover, by increasing the activation temperature, the specific surface area and pore volume increased, and pore size distribution shifted towards mesoporous structure. The Li-Se coin cell made from PWC activated at 600 °C (PWC600) demonstrated superior discharge capacity (640 mAh g–1 at 0.1C after 400 cycles), rate capability, and long cycling stability at higher current densities. The microporous features of PWC600 were crucial for effective Se confinement, lithium-ion diffusion, and charge transfer. This work emphasizes the sustainable development of microporous carbon from upcycled plastic waste as a promising cathode material for high-energy Li-Se batteries. Our findings contribute to environmentally friendly energy storage solutions and the circular economy by repurposing non-recyclable plastic waste into valuable materials.

Synthesis of hierarchical porous carbon scaffold derived from red kidney bean peels for advanced Li–Se and Na–Se batteries

Incorporating selenium into high-surface-area carbon with hierarchical pores, derived from red kidney bean peels via simple carbonization/activation, yields a superior Li–Se battery cathode material. This method produces a carbon framework with 568 m2 g−1 surface area, significant pore volume, and improves the composite’s electronic conductivity and stability by mitigating volume changes and reducing lithium polyselenide dissolution. The Se@ACRKB composite, containing 45 wt% selenium, shows high discharge capacities (609.13 mAh g−1 on the 2nd cycle, maintaining 470.76 mAh g−1 after 400 cycles at 0.2 C, and 387.58 mAh g−1 over 1000 cycles at 1 C). This demonstrates exceptional long-term stability and performance, also applicable to Na–Se batteries, with 421.36 mAh g−1 capacity after 200 cycles at 0.1 C. Our study showcases the potential of using sustainable materials for advanced battery technologies, emphasizing cost-effective and scalable solutions for energy storage.

Date seed-derived porous carbon for advanced Li–Se battery applications

Date seed-derived porous carbon for advanced Li–Se battery applications

Biometabolically Derived Selenium Nanoparticles Armed with Protein Protective Suit toward High-Performance Li-Se Batteries.

Selenium (Se) serves as a burgeoning high-energy-density cathode material in lithium-ion batteries. However, the development of Se cathode is strictly limited by low Se utilization and inferior cycling stability arising from intrinsic volume expansion and notorious shuttle effect. Herein, a microbial metabolism strategy is developed to prepare "functional vesicle-like" Se globules via Bacillus subtilis subsp. from selenite in sewage, in which Se nanoparticles are armed with a natural biological protein membrane with rich nitrogen and phosphorus, achieving the eco-efficient conversion of trash into treasure (selenite, SeO3 2- → Selenium, Se). The appealing-design "functional vesicle-like" Se globules are beneficial to accommodate volume changes of Se in electrochemical reactions, confining polyselenides via chemisorption, and enhancing mechanical strength of electrode by associated bacteria debris, realizing comprehensive utilization of microorganism. By conceptualizing "functional vesicle-like" Se globules, rather than artificial Se-host composites, as cathode for lithium-selenium batteries, it exhibits outstanding cycling stability and improved rate performance. This strategy opens the door to design smart electrode materials with unattainable structure that cannot be achieved by traditional approaches, achieving eco-efficient conversion of pollutants into energy-storage nanomaterials, which will be a promising research field for interdisciplinary of energy, biology, and environment.

Taming the anchor and conversion of polyselenides with a self-reinforcing host in lithium–selenium batteries

Energy-dense lithium–selenium (Li–Se) batteries have attracted increasing attention, while their practical application is still hindered, highly relating to the volume expansion and shuttle of Li polyselenides (LiPSes). Herein, a concurrent anchoring/converting strategy is proposed to restrain the dissolution and realize the rapid conversion of LiPSes. A prototypical regulator comprises of polar catalysts embedded in the interconnected porous muti-walled carbon network (i.e., CoSnO3 nanocubes/CNTs), which promises fast electron/ion transportation and inhibits volumetric effect. Moreover, CoSnO3 as redox accelerator enables the stretched Se−Se bonds to decrease the LiPSes bidirectional conversion barrier, achieving accelerated reaction kinetics. Consequently, the self-reinforcing optimized cathode exhibits superior initial capacity of 730 mAh/g, greatly enlarged capacity after 200 cycles (increase by ∼ 32 % than that of the cell with CNTs), and superior rate capacity (153 mAh/g at 2C). This work uncovers the roles of electronic/ionic conductivity and adsorption/catalysis in Li–Se batteries, providing a guidance for taming the utilization and kinetics of cathode from material perspectives.

High Selenium Loading in Vertically Aligned Porous Carbon Framework with Visualized Fast Kinetics for Enhanced Lithium/Sodium Storage

AbstractLithium/sodium–selenium (Li/Na–Se) batteries with high volumetric specific capacity are considered promising as next‐generation battery technologies. However, their practical application is hindered by challenges such as low Se loading in cathodes and the polyselenides shuttle effect. To address these challenges, a new Se host is introduced in the form of a free‐standing N, O co‐doped vertically aligned porous carbon framework decorated with a carbon nanotube forest (VCF‐CNTs), allowing for high mass loading of up to 16 mg cm−2. The low‐tortuosity Se@VCF‐CNTs architecture facilitates rapid lithiation/sodiation kinetics, while the CNT forests in vertical microchannels enhance efficient Se loading and serve as a multi‐layer fence to prevent undesired polyselenide shuttling. Consequently, the Se@VCF‐CNTs cathode displays a significant areal capacity of 10.3 mAh cm−2 at 0.1 C with a Se loading of 16 mg cm−2 for Li–Se batteries, exceeding that of commercial lithium ion batteries (4.0 mAh cm−2). In Na–Se batteries, the Se@VCF‐CNTs electrode with a Se loading of 5 mg cm−2 exhibits a discharge capacity of 436 mAh g−1 after 200 cycles, proving its consistent cycling performance. This study enriches the field of knowledge concerning high‐loading Se‐based battery systems, offering a promising avenue for enhancing energy density in the field.

Molybdenum single-atoms decorated multi-channel carbon nanofibers for advanced lithium-selenium batteries.

The cathode in lithium-selenium (Li-Se) batteries has garnered extensive attention owing to its superior specific capacity and enhanced conductivity compared to sulfur. Nonetheless, the adoption and advancement of Li-Se batteries face significant challenges due to selenium's low reactivity, substantial volume fluctuations, and the shuttle effect associated with polyselenides. Single-atom catalysts (SACs) are under the spotlight for their outstanding catalytic efficiency and optimal atomic utilization. To address the challenges of selenium's low chemical activity and volume expansion in Li-Se batteries, through electrospun, we have developed a lotus root-inspired carbon nanofiber (CNF) material, featured internal multi-channels and anchored with molybdenum (Mo) single atoms (Mo@CNFs). Mo single atoms significantly enhance the conversion kinetics of selenium (Se), facilitating rapid formation of Li2Se. The internally structured multi-channel CNF serves as an effective host matrix for Se, mitigating its volume expansion during the electrochemical process. The resulting cathode, Se/Mo@CNF composite, exhibits a high discharge specific capacity, superior rate performance, and impressive cycle stability in Li-Se batteries. After 500 cycles at a current density of 1 C, it maintains a capacity retention rate of 82% and nearly 100% coulombic efficiency (CE). This research offers a new avenue for the application of single-atom materials in enhancing advanced Li-Se battery performance.

In-situ texturing hollow carbon host anchored with Fe single atoms accelerating solid-phase redox for Li-Se batteries

Se-based cathodes have caught tremendous attention owing to their comparable volumetric capacity and better electronic conductivity to S cathodes. However, its low utilization ratio and sluggish redox kinetics due to the high reaction barrier of solid-phase transformation from Se to Li2Se limit its practical application. Herein, an in-situ texturing hollow carbon host by gas–solid interface reaction anchored with Fe single-atomic catalyst is designed and prepared for advanced Li-Se batteries. This Se host presents high pore volume of 1.49 cm3 g−1, Fe single atom content of 1.53 wt%, and its specific structure protects single-atomic catalyst from the destructive reaction environment, thus balancing catalytic activity and durability. After Se loading by reduction of H2SeO3, this homogenous Se-based cathode delivers a superior rate capacity of 431.3 mA h g−1 at 4C, and great discharge capacity of 301.8 mA h g−1 after 1000 cycles at 10C, with high Li-ion diffusion coefficient and capacitance-contributed ratio. The distribution of relaxation times analysis verifies solid-phase transformation mechanism of this cathode and density functional theory calculations confirm the adsorption and bidirectionally catalysis effect of Fe single-atomic catalyst. This work provides a new strategy to prepare high-efficient Se cathode associated with non-noble metal single atoms for high-performance Li-Se batteries.

2D ZIF-8 derived N-doped porous carbon nanosheets for high-performance Li-Se batteries

Lithium-selenium (Li-Se) batteries have attracted increasing attention because of excellent carbonate electrolyte compatibility, comparable theoretical volumetric specific capacity and high electrical conductivity. However, there are still unavoidable issues such as large volume expansion, rapid capacity decay and slow electrochemical reaction kinetics for practical applications. In this work, we report 2D ZIF-8 derived N-doped porous carbon nanosheets (NPC-NS) as Se host for high-performance Li-Se batteries. The unique 2D structure of Se@NPC-NS facilitates Li+ diffusion and charge transfer, thus the Se@NPC-NS cathode exhibits fast electrochemical reaction kinetics. In addition, the N doping enhances electronic conductivity and porous structure mitigates the volume expansion. As a result, the Se@NPC-NS cathode delivers a high reversible capacity of 585 mAh/g with a capacity retention of 99.1 % at 0.5C (1C = 675 mA g−1) after 225 cycles. Especially after 500 cycles at a high current density of 10C, the Se@NPC-NS cathode still displays a reversible specific capacity of 307 mAh/g with only 0.03 % capacity decay per cycle. This work would shed some light on the 2D carbon host as Se-based cathode for high-rate and long-life performance Li-Se batteries.

From longan peel waste to energy storage: Porous activated carbon as a cathode matrix for advanced Li/Na-selenium batteries

This paper explores the potential of Longan peel waste (LPw) as a sustainable and cost-effective matrix for selenium-based cathodes in Li-Se and Na-Se batteries. Following activation, we created LP2—a designation for the carbon precursor derived from LPw, activated at a 1:2 ratio of carbonized LPw to KOH. This nomenclature, where ‘LP' stands for ‘Longan peel' and ‘2′ reflects the optimization of this ratio, led to a hierarchical porous structure with an average pore size of 3.0307 ​nm and a significant BET surface area of 111.9386 ​m2 ​g-1. Selenium was incorporated into the LP2 matrix using a simple melt diffusion technique, yielding the composite Se@LP2. In Li-Se batteries, Se@LP2 exhibited an initial discharge capacity of 1033.75 mAh g⁻1 ​at 0.1C. At a 1C rate, the composite demonstrated a capacity retention of 301.14 mAh g⁻1 after 550 cycles and 380.91 mAh g⁻1 after 100 cycles. Moreover, for Na-Se batteries, the composite showcased a capacity retention of 347.18 mAh g⁻1 after 100 cycles at 0.1C. These findings underscore LP2's potential as a viable and efficient matrix for selenium-based cathodes, revealing promising prospects for the advancement of highly efficient Li-Se and Na-Se batteries.

In-situ confining selenium within bubble - like carbon nanoshells for ultra-stable Li-Se batteries.

Lithium-selenium (Li-Se) batteries are promising energy storage devices. However, the long-term durability and high-rate performance of the Se cathode have been limited by significant volume expansion and the troublesome shuttle effect of polyselenides during repeated charging/discharging processes. To revolutionize these issues, we applied a top-down strategy through the in-situ trapping of amorphous Se within bubble-like carbon (BLC) frameworks, which can radically minimize the presence of surface-absorbed Se while enhancing Se loading capacity. This ingenious technique successfully encapsulates all Se species within carbon nanoshells, creating a distinct half-filled core-shell structure known as Se@void@BLC. This in-situ trapping approach ensures the efficient management of Se volume changes during repeated discharge and charge cycles. Moreover, an extraordinary Se loading capacity of up to 65.6 wt% is reached. Using the Se@void@BLC as cathode for Li-Se battery, we achieve a high initial Columbic efficiency of 84.2 %, a high reversible capacity of 585 mAh g-1 , and an ultralow capacity decay of only 0.0037 % per cycle during 4000 cycles at 10 A g-1 .

High performance all-solid-state Li–Se battery based on selenium loaded on Ti3C2 MXene cathode

Selenium has high theoretical volumetric capacity of 3253 mAh cm−3 and acceptable electronic conductivity of 1 × 10−5 S m−1, which is considered as a potential alternative to sulfur cathode for all-solid-state rechargeable batteries with high energy density. However, the development of all-solid-state Li–Se batteries (ASSLSBs) are hindered by sluggish kinetics and poor cycling life. In this work, trigonal Se nanocrystallines are homogenously distributed in the interspace and on the surface of MXene layers (denoted as Se@MXene composite) by a novel melt-diffusion method. ASSLSBs based on this Se@MXene composite cathode exhibit large specific capacity of 632 mAh g−1 at 0.05 A g−1, high-rate capability over 4 A g−1, and excellent cycling stability over 300 cycles at 1 A g−1. The ex-situ analytical techniques demonstrate that the excellent electrochemical performance of Se@MXene cathode largely arises from structural stability with the assistance of conductive MXene and reversible redox behavior between Li2Se and Se during the repeating charge/discharge process. Our study points out the potential of material design of Se cathode based on conducting 2D materials with good electrochemical behavior, which may accelerate the practicability of ASSLSBs.

Natural okra gum as functional binder enables highly stable Lithium–Selenium batteries

Lithium–selenium (Li–Se) batteries are garnered significant attention due to their high theoretical specific capacity, high volumetric energy density and moderate output voltage. Nevertheless, Li–Se batteries are still restricted by severe volume expansion and “shuttle effect” of polyselenides, resulting in deteriorated electrochemical performance. Binders are a crucial component of Li–Se batteries, playing a key role in addressing the mentioned issues. Herein, a non-toxic, bio-friendly, hydro-soluble binder of okra gum (OG) extracted from okra pods is proposed to ameliorate the electrochemical performance of Li–Se batteries. The as-prepared OG binders are rich in branched-chain polysaccharides (glucoside) and polar functional groups (–C–O–C–, –COOH), which not only have a good interpenetrating binding network to ensure the mechanical stability of Se cathode, but also have excellent interfacial chemical binding force for immobilizing polyselenides. Consequently, the OG binder endows Li–Se batteries with high initial discharge capacity (607 mA h g−1 at 0.2C), good cycling stability (218 mA h g−1 after 100 cycles at 0.2C), and remarkable rate performance (364 mA h g−1 at 1C), all of which are superior to Li–Se batteries with PVDF binder. Our study demonstrates the feasibility of natural mucilage as functional binder for Li–Se batteries and paves a research path in developing natural plant-based binders to stabilize electrode materials for reliable high-energy batteries.

Integration of a composite polymer electrolyte and Se/C cathodes toward high-performance all-solid-state Li–Se batteries

The coupling of composite polymer electrolytes with Se/C cathodes was achieved in this study to address the needs of modern solid-state batteries, including high-energy density, low temperature operation, cycle stability, and ease of manufacture.

A dual-functional matrix with high absorption and electrocatalysis to suppress the shuttle effect in lithium–selenium batteries

A dual-functional matrix as both an adsorbent and an electrocatalyst effectively restrained the shuttle effect and improved the electrochemical performance of Li–Se batteries.

Carbon spheres with catalytic silver centres as selenium hosts for stable lithium–selenium batteries

A silver-centred carbon host for a Li–Se battery cathode is developed by a simple microwave-assisted approach. The successful immobilization of polyselenides by silver catalyst within the pores of the carbon spheres offers improved cycling stability.

Anchoring and catalytic insights into bilayer C4N3 material for lithium-selenium batteries: a first-principles study.

In the present work, a theoretical design for the viability of bilayer C4N3 (bi-C4N3) as a promising host material for Li-Se battery was conducted utilizing first-principles calculations. The AA- and AB-stacking configurations of bilayer C4N3 can effectively inhibit the shuttling of high-order polyselenides through the synergistic effect of physical confinement and strong Li-N bonds. Compared to conventional electrolytes, the AA- and AB-stacking bilayer C4N3 demonstrate enhanced adsorption capabilities for the polyselenides. The anchored structures of Se8 or Li2Sen (n = 1, 2, 4, 6, 8) molecules within the bilayer C4N3 exhibit high electrical conductivities, which are beneficial for enhancing the electrochemical performance. The catalytic effects of AA- and AB-stacking bilayer C4N3 were investigated by the reduction of Se8 and the energy barrier associated with the decomposition of Li2Se. The AA- and AB-stacking bilayer C4N3 can significantly decrease the activation barrier and promote the decomposition of Li2Se. The mean square displacement (MSD) curves reveal the pronounceably sluggish Li-ions diffusions in polyselenides within the AA- and AB-stacking bilayer C4N3, which in turn demonstrates the notable prospects in mitigating the shuttle effect.