RESUMEN
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- â 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.
RESUMEN
Lithium-sulfur (Li-S) batteries are expected to be the next-generation energy storage system due to the ultrahigh theoretical energy density and low cost. However, the notorious shuttle effect of higher-order polysulfides and the uncontrollable lithium dendrite growth are the two biggest challenges for commercially viable Li-S batteries. Herein, these two main challenges are solved by in situ polymerization of bi-functional gel polymer electrolyte (GPE). The initiator (SiCl4) not only drives the polymerization of 1,3-dioxolane (DOL) but also induces the construction of a hybrid solid electrolyte interphase (SEI) with inorganic-rich compositions on the Li anode. In addition, diatomaceous earth (DE) is added and anchored in the GPE to obtain PDOL-SiCl4-DE electrolyte through in situ polymerization. Combined with density functional theory (DFT) calculations, the hybrid SEI provides abundant adsorption sites for the deposition of Li+, inhibiting the growth of lithium dendrites. Meanwhile, the shuttle effect is greatly alleviated due to the strong adsorption capacity of DE toward lithium polysulfides. Therefore, the Li/Li symmetric cell and Li-S full cell assembled with PDOL-SiCl4-DE exhibit excellent cycling stability. This study offers a valuable reference for the development of high performance and safe Li-S batteries.
RESUMEN
High-performance lithium metal anodes are crucial for the development of advanced Li metal batteries. Herein, this work reports a novel plasma coupled electrolyte additive strategy to prepare high-quality composite solid electrolyte interphase (SEI) on Li metal to achieve enhanced performance and stability. With the guidance of calculations, this work selects diethyl dibromomalonate (DB) as an additive to optimize the solvation structure of electrolytes to modify the SEI. Meanwhile, this work groundbreakingly develops DB plasma technology coupled with DB electrolyte additive to construct a combinatorial SEI: inner plasma-induced SEI layer composed of LiBr and Li2CO3 plus additive-reduced SEI containing LiBr/Li2CO3/organic lithium compounds as an outer compatible layer. The optimized hybrid SEI has strong affinity toward Li+ and good mechanical properties, thereby inducing horizontal dispersion and uniform deposition of Li+ and keep structure stable. Accordingly, the symmetrical cells exhibit enhanced cycling stability for 1200 h at an overpotential of 23.8 mV with average coulombic efficiency (99.51%). Additionally, the full cells with LiNi0.8Co0.1Mn0.1O2 cathode deliver a capacity retention of 81.7% after 300 cycles at 0.5 C, and the pouch cell achieves a volumetric specific energy of ≈664 Wh Lâ1. This work provides new enlightenment on plasma technology for fabrication of advanced metal anodes for energy storage.
RESUMEN
Unfavorable parasitic reactions between the Ni-rich layered oxide cathode and the sulfide solid electrolyte have plagued the realization of all-solid-state rechargeable Li batteries. The accumulation of inactive by-products (P2Sx, S, POx n- and SOx n-) at the cathode-sulfide interface impedes fast Li-ion transfer, which accounts for sluggish reaction kinetics and significant loss of cathode capacity. Herein, we proposed an easily scalable approach to stabilize the cathode electrochemistry via coating the cathode particles by a uniform, Li+-conductive plastic-crystal electrolyte nanolayer on their surface. The electrolyte, which simply consists of succinonitrile and Li bis(trifluoromethanesulphonyl)imide, serves as an interfacial buffer to effectively suppress the adverse phase transition in highly delithiated cathode materials, and the loss of lattice oxygen and generation of inactive oxygenated by-products at the cathode-sulfide interface. Consequently, an all-solid-state rechargeable Li battery with the modified cathode delivers high specific capacities of 168â mAh g-1 at 0.1â C and a high capacity retention >80 % after 100 cycles. Our work sheds new light on rational design of electrode-electrolyte interface for the next-generation high-energy batteries.
RESUMEN
Sulfide-based all-solid-state lithium batteries (ASSLBs) have attracted unprecedented attention in the past decade due to their excellent safety performance and high energy storage density. However, the sulfide solid-state electrolytes (SSEs) as the core component of ASSLBs have a certain stiffness, which inevitably leads to the formation of pores and cracks during the production process. In addition, although sulfide SSEs have high ionic conductivity, the electrolytes are unstable to lithium metal and have non-negligible electronic conductivity, which severely limits their practical applications. Herein, a grain boundary electronic insulation strategy through in situ polymer encapsulation is proposed for this purpose. A polymer layer with insulating properties is applied to the surface of the Li5.5PS4.5Cl1.5 (LPSC) electrolyte particles by simple ball milling. In this way, we can not only achieve a dense electrolyte pellet but also improve the stability of the Li metal anode and reduce the electronic conductivity of LPSC. This strategy of electronic isolation of the grain boundaries enables stable deposition/stripping of the modified electrolyte for more than 2000 h at a current density of 0.5 mA cm-1 in a symmetrical Li/Li cell. With this strategy, a full cell with Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) as the cathode shows high performance including high specific capacity, improved high-rate capability, and long-term stability. Therefore, this study presents a new strategy to achieve high-performance sulfide SSEs.
RESUMEN
The design and fabrication of a lithiophilic skeleton are highly important for constructing advanced Li metal anodes. In this work, a new lithiophilic skeleton is reported by planting metal sulfides (e.g., Ni3S2) on vertical graphene (VG) via a facile ultrafast Joule heating (UJH) method, which facilitates the homogeneous distribution of lithiophilic sites on carbon cloth (CC) supported VG substrate with firm bonding. Ni3S2 nanoparticles are homogeneously anchored on the optimized skeleton as CC/VG@Ni3S2, which ensures high conductivity and uniform deposition of Li metal with non-dendrites. By means of systematic electrochemical characterizations, the symmetric cells coupled with CC/VG@Ni3S2 deliver a steady long-term cycle within 14 mV overpotential for 1800 h (900 cycles) at 1 mA cm-2 and 1 mAh cm-2. Meanwhile, the designed CC/VG@Ni3S2-Li||LFP full cell shows notable electrochemical performance with a capacity retention of 92.44% at 0.5 C after 500 cycles and exceptional rate performance. This novel synthesis strategy for metal sulfides on hierarchical carbon-based materials sheds new light on the development of high-performance lithium metal batteries (LMBs).
RESUMEN
Uneven lithium (Li) metal deposition typically results in uncontrollable dendrite growth, which renders an unsatisfactory cycling stability and coulombic efficiency (CE) of Li metal batteries (LMBs), preventing their practical application. Herein, a novel carbon cloth with the modification of ZnO nanosheets (ZnO@CC) is fabricated for LMBs. The as-prepared ZnO@CC with a cross-linked network significantly reduces the local current density, and the design of ZnO nanosheets can promote the uniform deposition of Li metal as lithiophilic sites. As a result, the Li metal anodes (LMAs) based on ZnO@CC (ZnO@CC@Li) enables a long cycle life over 640â hours with a low overpotential of 65â mV at a current density of 4â mA cm-2 with a capacity of 1â mAh cm-2 in the symmetric cell. Moreover, when coupling the ZnO@CC@Li with a LiFePO4 cathode, the assembled full cell exhibits excellent long cycle and rate performance, highlighting its promising practical application prospect.
RESUMEN
All-solid-state lithium batteries (ASSLBs) are attracting tremendous attention due to their improved safety and higher energy density. However, the use of a metallic lithium anode poses a major challenge due to its low stability and processability. Instead, the graphite anode exhibits high reversibility for the insertion/deinsertion of lithium ions, giving ASSLBs excellent cyclic stability but a lower energy density. To increase the energy density of ASSLBs with the graphite anode, it is necessary to lower the negative/positive (N/P) capacity ratio and to increase the charging voltage. These strategies bring new challenges to lithium metal plating and dendrite growth. Here, a nano-Ag-modified graphite composite electrode (Ag@Gr) is developed to overcome these shortcomings for Li5.5PS4.5Cl1.5-based ASSLBs. The Ag@Gr composite exhibits a strong ability to inhibit lithium metal plating and fast lithium-ion transport kinetics. Ag nanoparticles can accommodate excess Li, and the as-obtained Li-Ag alloy enhances the kinetics of the composite electrode. The ASSLB with the Li(Ni0.8Co0.1Mn0.1)O2 cathode and Ag@Gr anode achieves an energy density of 349 W h kg-1. The full cell using Ag@Gr with an N/P ratio of 0.6 also highlights the rate performance. This work provides a simple and effective method to regulate the charge transport kinetics of graphite anodes and improve the cyclic performance and energy density of ASSLBs.
RESUMEN
Bacterial infections in wounds continue to be a major challenge in clinical settings worldwide and represent a significant threat to human health. This work proposes novel expandable and versatile methods for solidifying sodium alginate (SA) with metal ions (such as Fe3+, Co2+, Ni2+, Cu2+, and Zn2+) to create Metal-Alginate (M-Alg) hydrogel with adjustable morphology, composition, and microstructure. It conforms to the wound site, protects against second infection, reduces inflammation, and promotes the healing of infected wounds. Among these hydrogels, Cu-Alginate (Cu-Alg) shows excellent sterilization effect and good efficacy against both gram-positive and gram-negative bacteria, including multidrug-resistant (MDR) strains such as Methicillin-resistant Staphylococcus aureus (MRSA) and Carbapenem-resistant Klebsiella pneumoniae (CRKP) due to its dual antibacterial mechanisms: contact-killing and reactive oxygen species (ROS) burst. Importantly, it exhibits low cytotoxicity and biodegradability. This simple and cost-effective gel-based system has the potential to introduce an innovative approach to the management of wound infection and offers promising new perspectives for the advancement of wound care practice.
Asunto(s)
Alginatos , Antibacterianos , Hidrogeles , Staphylococcus aureus Resistente a Meticilina , Infección de Heridas , Alginatos/química , Hidrogeles/química , Hidrogeles/farmacología , Infección de Heridas/tratamiento farmacológico , Infección de Heridas/microbiología , Animales , Antibacterianos/química , Antibacterianos/farmacología , Staphylococcus aureus Resistente a Meticilina/efectos de los fármacos , Ratones , Klebsiella pneumoniae/efectos de los fármacos , Cicatrización de Heridas/efectos de los fármacos , Metales/química , Humanos , Piel/efectos de los fármacos , Piel/microbiología , Especies Reactivas de Oxígeno/metabolismo , Iones/químicaRESUMEN
All-solid-state lithium-sulfur batteries (ASSLSBs) have attracted wide attention due to their ultrahigh theoretical energy density and the ability of completely avoiding the shuttle effect. However, the further development of ASSLSBs is limited by the poor kinetic properties of the solid electrode interface. It remains a great challenge to achieve good kinetic properties, by common strategies to substitute sulfur-transition metal and organosulfur composites for sulfur without reducing the specific capacity of ASSLSBs. In this study, a sulfur-(Ketjen Black)-(bistrifluoromethanesulfonimide lithium salt) (S-KB-LiTFSI) composite is constructed by introducing LiTFSI into the S-KB composite. The initial discharge capacity reaches up to 1483 mA h g-1, benefited from the improved ionic conductivity and diffusion kinetics of the S-KB-LiTFSI composite, where numerous LiF interphases with a Li3N component are in situ formed during cycling. Combined with DFT calculations, it is found that the migration barriers of LiF and Li3N are much smaller than that of the Li6PS5Cl solid electrolyte. The fast ionic conductors of LiF and Li3N not only enhance the Li+ transfer efficiency but also improve the interfacial stability. Therefore, the assembled ASSLSBs operate stably for 600 cycles at 200 mA g-1, and this study provides an effective strategy for the further development of ASSLSBs.
RESUMEN
The construction of high-quality carbon-based energy materials through biotechnology has always been an eager goal of the scientific community. Herein, juice vesicles bioreactors (JVBs) bio-technology based on hesperidium (e.g., pomelo, waxberry, oranges) is first reported for preparation of carbon-based composites with controllable components, adjustable morphologies, and sizes. JVBs serve as miniature reaction vessels that enable sophisticated confined chemical reactions to take place, ultimately resulting in the formations of complex carbon composites. The newly developed approach is highly versatile and can be compatible with a wide range of materials including metals, alloys, and metal compounds. The growth and self-assembly mechanisms of carbon composites via JVBs are explained. For illustration, NiCo alloy nanoparticles are successfully in situ implanted into pomelo vesicles crosslinked carbon (PCC) by JVBs, and their applications as sulfur/carbon cathodes for lithium-sulfur batteries are explored. The well-designed PCC/NiCo-S electrode exhibits superior high-rate properties and enhanced long-term stability. Synergistic reinforcement mechanisms on transportation of ions/electrons of interface reactions and catalytic conversion of lithium polysulfides arising from metal alloy and carbon architecture are proposed with the aid of DFT calculations. The research provides a novel biosynthetic route to rational design and fabrication of carbon composites for advanced energy storage.
RESUMEN
"Carbon Peak and Carbon Neutrality" is an important strategic goal for the sustainable development of human society. Typically, a key means to achieve these goals is through electrochemical energy storage technologies and materials. In this context, the rational synthesis and modification of battery materials through new technologies play critical roles. Plasma technology, based on the principles of free radical chemistry, is considered a promising alternative for the construction of advanced battery materials due to its inherent advantages such as superior versatility, high reactivity, excellent conformal properties, low consumption and environmental friendliness. In this perspective paper, we discuss the working principle of plasma and its applied research on battery materials based on plasma conversion, deposition, etching, doping, etc. Furthermore, the new application directions of multiphase plasma associated with solid, liquid and gas sources are proposed and their application examples for batteries (e. g. lithium-ion batteries, lithium-sulfur batteries, zinc-air batteries) are given. Finally, the current challenges and future development trends of plasma technology are briefly summarized to provide guidance for the next generation of energy technologies.
RESUMEN
The design and fabrication of novel carbon hosts with high conductivity, accelerated electrochemical catalytic activities, and superior physical/chemical confinement on sulfur and its reaction intermediates polysulfides are essential for the construction of high-performance C/S cathodes for lithium-sulfur batteries (LSBs). In this work, a novel biofermentation coupled gel composite assembly technology is developed to prepare cross-linked carbon composite hosts consisting of conductive Rhizopus hyphae carbon fiber (RHCF) skeleton and lamellar sodium alginate carbon (SAC) uniformly implanted with polarized nanoparticles (V2O3, Ag, Co, etc.) with diameters of several nanometers. Impressively, the RHCF/SAC/V2O3 composites exhibit enhanced physical/chemical adsorption of polysulfides due to the synergistic effect between hierarchical pore structures, heteroatoms (N, P) doping, and polar V2O3 generation. Additionally, the catalytic conversion kinetics of cathodes are effectively improved by regulating the 3D carbon structure and optimizing the V2O3 catalyst. Consequently, the LSBs assembled with RHCF/SAC/V2O3-S cathode show exceptional cycle stability (capacity retention rate of 94.0% after 200 cycles at 0.1 C) and excellent rate performance (specific capacity of 578 mA h g-1 at 5 C). This work opens a new door for the fabrication of hyphae carbon composites via fermentation for electrochemical energy storage.
RESUMEN
All-solid-state lithium metal batteries (LMBs) are regarded as one of the most viable energy storage devices and their comprehensive properties are mainly controlled by solid electrolytes and interface compatibility. This work proposes an advanced poly(vinylidene fluoride-hexafluoropropylene) based gel polymer electrolyte (AP-GPEs) via functional superposition strategy, which involves incorporating butyl acrylate and polyethylene glycol diacrylate as elastic optimization framework, triethyl phosphate and fluoroethylene carbonate as flameproof liquid plasticizers, and Li7La3Zr2O12 nanowires (LLZO-w) as ion-conductive fillers, endowing the designed AP-GPEs/LLZO-w membrane with high mechanical strength, excellent flexibility, low flammability, low activation energy (0.137 eV), and improved ionic conductivity (0.42 × 10-3 S cm-1 at 20 °C) due to continuous ionic transport pathways. Additionally, the AP-GPEs/LLZO-w membrane shows good safety and chemical/electrochemical compatibility with the lithium anode, owing to the synergistic effect of LLZO-w filler, flexible frameworks, and flame retardants. Consequently, the LiFePO4/Li batteries assembled with AP-GPEs/LLZO-w electrolyte exhibit enhanced cycling performance (87.3% capacity retention after 600 cycles at 1 C) and notable high-rate capacity (93.3 mAh g-1 at 5 C). This work proposes a novel functional superposition strategy for the synthesis of high-performance comprehensive GPEs for LMBs.
RESUMEN
Titanium dioxide (TiO2) has been widely used as an alternative anodic material for lithium-ion batteries (LIBs) due to its ultrahigh capacity retention and long cycle lifespan. However, the restriction of lithium insertion, intrinsically poor electronic conductivity, and sluggish lithium ionic kinetics of bulk TiO2 hinder their specific capacity and rate performance. Herein, LiTiO2 nanoparticles (NPs) are synthesized via a facile ball milling method by the reaction of anatase TiO2 with LiH. The as-prepared LiTiO2 NPs have strong structural stability and a "zero strain" effect during the repeated intercalation/deintercalation, even at low potential. As anodic materials for LIBs, LiTiO2 NPs exhibit a superior rate performance of â¼100 mA h g-1 at 10C (3350 mA g-1) with a capacity retention of 100% after 1000 cycles, which is 5 times higher than that of the original commercial anatase TiO2 powder. The higher specific capacity of LiTiO2 NPs is attributed to the increased conversion of Ti3+ to Ti2+ on the porous surface of LiTiO2 NPs, which provides a more capacitive contribution. This study not only provides a new fabrication approach toward Ti-based anodes for ultrafast LIBs but also underscores the potential importance of embedding lithium into transition metal oxides as a strategy for boosting their electrochemical performance.
RESUMEN
Developing high-efficiency and easy machining components, as well as high-performance energy storage components, is a pressing issue on the road to economic and social progress. Optimizing the interface compatibility between composites and promoting the efficient utilization of the electrochemical active sites are crucial factors in improving the electrochemical performance of composite electrode materials. To address this challenge, a carbon-based flexible lithium-ion supercapacitor positive material (Polyaniline @ Carbon Foam-Supercritical carbon dioxide (P@C-SC)) is synthesized using commercial melamine foam and aniline monomer. The synthesis process utilizes supercritical fluid technology, effectively solving the interface compatibility problem between the composite materials. Consequently, the electrochemical performance of the composite electrode materials is significantly improved. The supercapacitive properties of this material are investigated in 1 mol/L sulfuric acid (H2SO4) and lithium sulfate (Li2SO4) electrolytes using a three-electrode system. In H2SO4 electrolyte, the material exhibits a working voltage of up to 2.2 V and a specific capacitance of 898F/g (at 1 A/g), resulting in a maximum energy density of 50.8 Wh kg-1. Furthermore, this electrode demonstrates superior lithium storage performance, with a specific capacity of approximately 900 mAh/g (at 1 A/g) and a retention of about 400 mAh/g after 200 cycles, along with a coulomb efficiency of 100%. This work offers insights into the integrated design of composite materials with improved electrochemical properties and interface compatibility, thus providing potential applicability of supercritical fluids in the field of lithium-ion supercapacitors.
RESUMEN
Lithium (Li) metal is considered as a promising anode candidate for high-energy-density batteries. However, the high reactivity of Li metal leads to poor air stability, limiting its practical application. Additionally, the interfacial instability, such as dendrite growth and an unstable solid electrolyte interphase layer, further complicates its utilization. Herein, a dense lithium fluoride (LiF)-rich interfacial protective layer is constructed on the Li surface through a simple reaction between Li and fluoroethylene carbonate (denoted as LiF@Li). The LiF-rich interfacial protective layer consists of both organic (ROCO2Li and C-F-containing species, which only exist on the outer layer) and inorganic (LiF and Li2CO3, distribute throughout the layer) components with a thickness of â¼120 nm. Specifically, chemically stable LiF and Li2CO3 play an important role in blocking air and hence improve the air durability of LiF@Li anodes. Notably, LiF with high Li+ diffusivity facilitates uniform Li+ deposition, while organic components with high flexibility relieve volume change upon cycling, thereby enhancing the dendrite inhibition capacity of LiF@Li. Consequently, LiF@Li exhibits remarkable stability and excellent electrochemical performance in both symmetric cells and LiFePO4 full cells. Moreover, LiF@Li maintains its initial color and morphology even after air exposure for 30 min, and the air-exposed LiF@Li anode still retains its superior electrochemical performance, further establishing its outstanding air-defendable capability. This work proposes a facile approach in constructing air-stable and dendrite-free Li metal anodes toward reliable Li metal batteries.
RESUMEN
The use of poly(1,3-dioxolane) (PDOL) electrolyte for lithium batteries has gained attention due to its high ionic conductivity, low cost, and potential for large-scale applications. However, its compatibility with Li metal needs improvement to build a stable solid electrolyte interface (SEI) toward metallic Li anode for practical lithium batteries. To address this concern, this study utilized a simple InCl3 -driven strategy for polymerizing DOL and building a stable LiF/LiCl/LiIn hybrid SEI, confirmed through X-ray photoelectron spectroscopy (XPS) and cryogenic-transmission electron microscopy (Cryo-TEM). Furthermore, density functional theory (DFT) calculations and finite element simulation (FES) verify that the hybrid SEI exhibits not only excellent electron insulating properties but also fast transport properties of Li+ . Moreover, the interfacial electric field shows an even potential distribution and larger Li+ flux, resulting in uniform dendrite-free Li deposition. The use of the LiF/LiCl/LiIn hybrid SEI in Li/Li symmetric batteries shows steady cycling for 2000 h, without experiencing a short circuit. The hybrid SEI also provided excellent rate performance and outstanding cycling stability in LiFePO4 /Li batteries, with a high specific capacity of 123.5 mAh g-1 at 10 C rate. This study contributes to the design of high-performance solid lithium metal batteries utilizing PDOL electrolytes.
RESUMEN
The implementation of all-solid-state lithium batteries (ASSLBs) is regarded as an important step toward the next-generation energy storage systems. The sulfide solid-state electrolyte (SSE) is a promising candidate for ASSLBs due to its high ionic conductivity and easy processability. However, the interface stability of sulfide SSEs toward high-capacity cathodes like nickel-rich layered cathodes is limited by the interfacial side reaction and narrow electrochemical window of the electrolyte. Herein, we propose introducing the halide SSE Li3InCl6 (LIC) with high (electro)chemical stability and superior Li+ conductivity to act as an ionic conductive additive in the Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM) cathode mixture through a slurry coating, aiming to build a stable cathode-electrolyte interface. This work demonstrates that the sulfide SSE Li5.5PS4.5Cl1.5 (LPSCl) is chemically incompatible with the NCM cathode, and the indispensable role of the substitution of LPSCl with LIC in enhancing the interfacial compatibility and oxidation stability of the electrolyte is highlighted. Accordingly, this new configuration shows superior electrochemical performance at room temperature. It shows a high initial discharge capacity (136.3 mA h g-1 at 0.1C), cycling performance (77.4% capacity retention at the 100th cycle), and rate capability (79.3 mA h g-1 at 0.5C). This work paves the way for investigating interfacial challenges regarding high-voltage cathodes and provides new insights into possible interface engineering strategies.