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Sub-nanoclusters with ultra-small particle sizes are particularly significant to create advanced energy storage materials. Herein, Sn sub-nanoclusters encapsulated in nitrogen-doped multichannel carbon matrix (denoted as Sn-SCs@MCNF) are designed by a facile and controllable route as flexible anode for high-performance potassium ion batteries (PIBs). The uniformly dispersed Sn sub-nanoclusters in multichannel carbon matrix can be precisely identified, which ensure us to clarify the size influence on the electrochemical performance. The sub-nanoscale effect of Sn-SCs@MCNF restrains electrode pulverization and enhances the K+ diffusion kinetics, leading to the superior cycling stability and rate performance. As freestanding anode in PIBs, Sn-SCs@MCNF manifests superior K+ storage properties, such as exceptional cycling stability (331 mAh g-1 after 150 cycles at 100 mA g-1) and rate capability. Especially, the Sn-SCs@MCNF||KFe[Fe(CN)6] full cell demonstrates impressive reversible capacity of 167 mAh g-1 at 0.4 A g-1 even after 200 cycles. Theoretical calculations clarify that the ultrafine Sn sub-nanoclusters are beneficial for electron transfer and contribute to the lower energy barriers of the intermediates, thereby resulting in promising electrochemical performance. Comprehensive investigation for the intrinsic K+ storage process of Sn-SCs@MCNF is revealed by in situ analysis. This work provides vital guidance to design sub-nanoscale functional materials for high-performance energy-storage devices.
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Silicon monoxide (SiO) has attracted considerable interest as anode material for lithium-ion batteries (LIBs). However, their poor initial Coulombic efficiency (ICE) and conductivity limit large-scale applications. Prelithiation and carbon-coating are common and effective strategies in industry for enhancing the electrochemical performance of SiO. However, the involved heat-treatment processes inevitably lead to coarsening of active silicon phases, posing a significant challenge in industrial applications. Herein, the differences in microstructures and electrochemical performances between prelithiated SiO with a pre-coated carbon layer (SiO@C@PLi) and SiO subjected to carbon-coating after prelithiation (SiO@PLi@C) are investigated. A preliminary carbon layer on the surface of SiO before prelithiation is found that can suppress active Si phase coarsening effectively and regulate the post-prelithiation phase content. The strategic optimization of the sequence where prelithiation and carbon-coating processes of SiO exert a critical influence on its regulation of microstructure and electrochemical performances. As a result, SiO@C@PLi exhibits a higher ICE of 88.0%, better cycling performance and lower electrode expansion than SiO@PLi@C. The pouch-type full-cell tests demonstrate that SiO@C@PLi/Graphite||NCM811 delivers a superior capacity retention of 91% after 500 cycles. This work provides invaluable insights into industrial productions of SiO anodes through optimizing the microstructure of SiO in prelithiation and carbon-coating processes.
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Vanadium-based phosphate cathode materials (e.g., K3V2(PO4)3) have attracted widespread concentration in cathode materials in potassium-ion batteries owing to their stable structure but suffer from low capacity and poor conductivity. In this work, an element doping strategy is applied to promote its electrochemical performance so that K3.2V2.8Mn0.2(PO4)4/C is prepared via a simple sol-gel method. The heterovalent Mn2+ is introduced to stimulated multiple electron reactions to improve conductivity and capacity, as well as interlayer spacing. Galvanostatic intermittent titration technique (GITT) and in situ X-ray diffraction results further confirm that Mn-doping in the original electrode can obtain superior electrode process kinetics and structural stability. The prepared K3.2V2.8Mn0.2(PO4)4/C exhibits a high-capacity retention of 80.8% after 1 500 cycles at 2 C and an impressive rate capability, with discharge capacities of 87.6 at 0.2 C and 45.4 mA h g-1 at 5 C, which is superior to the majority of reported vanadium-based phosphate cathode materials. When coupled K3.2V2.8Mn0.2(PO4)4/C cathode with commercial porous carbon (PC) anode as the full cell, a prominent energy density of 175 Wh kg-1 is achieved based on the total active mass. Overall, this study provides an effective strategy for meliorating the cycling stability and capacity of the polyanion cathodes for KIB.
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Alkali metals (Li, Na, and K) are deemed as the ideal anode materials for next-generation high-energy-density batteries because of their high theoretical specific capacity and low redox potentials. However, alkali metal anodes (AMAs) still face some challenges hindering their further applications, including uncontrollable dendrite growth and unstable solid electrolyte interphase during cycling, resulting in low Coulombic efficiency and inferior cycling performance. In this regard, designing 3D current collectors as hosts for AMAs is one of the most effective ways to address the above-mentioned problems, because their sufficient space could accommodate AMAs' volume expansion, and their high specific surface area could lower the local current density, leading to the uniform deposition of alkali metals. Herein, we review recent progress on the application of 3D Cu-based current collectors in stable and dendrite-free AMAs. The most widely used modification methods of 3D Cu-based current collectors are summarized. Furthermore, the relationships among methods of modification, structure and composition, and the electrochemical properties of AMAs using Cu-based current collectors, are systematically discussed. Finally, the challenges and prospects for future study and applications of Cu-based current collectors in high-performance alkali metal batteries are proposed.
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Aqueous zinc-ion batteries (AZIBs) are widely regarded as desirable energy storage devices due to their inherent safety and low cost. Hydrogel polymer electrolytes (HPEs) are cross-linked polymers filled with water and zinc salts. They are not only widely used in flexible batteries but also represent an ideal electrolyte candidate for addressing the issues associated with the Zn anode, including dendrite formation and side reactions. In HPEs, an abundance of hydrophilic groups can form strong hydrogen bonds with water molecules, reducing water activity and inhibiting water decomposition. At the same time, special Zn2+ transport channels can be constructed in HPEs to homogenize the Zn2+ flux and promote uniform Zn deposition. However, HPEs still face issues in practical applications, including poor ionic conductivity, low mechanical strength, poor interface stability, and narrow electrochemical stability windows. This Review discusses the issues associated with HPEs for advanced AZIBs, and the recent progresses are summarized. Finally, the Review outlines the opportunities and challenges for achieving high performance HPEs, facilitating the utilization of HPEs in AZIBs.
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We designed and prepared the ZnSe/CoSe2@NC/CNTs (ZCNC) cathode material for aluminum batteries (ABs). The ZCN (ZnSe/CoSe2@NC) is connected by the interwoven carbon nanotube (CNT) conductive network to form a beaded structure. CNTs and the carbon formed by carbonization of organic ligands is beneficial to improving the electrical conductivity of the material and reducing structural damage during cycling. The internal electric field generated at the interface of heterostructures can promote the transfer of electrons/ions. This special structure promotes ZCNC excellent electrochemical properties. At 100 mA/g, the specific capacity of the first discharge reaches 338 mAh/g, while the specific capacity after 500 cycles still reaches 217 mAh/g. Compared with ZCN and CN(CoSe2@NC), it demonstrates a great advantage.
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Biochar is commonly utilized as an electrode material in supercapacitors. However, the conventional carbonization process often results in macromolecular compounds, which obstruct the porous structure of carbon materials, thereby reducing their capacitance. Dielectric barrier discharge low-temperature plasma (DLTP) is a technology that transforms gases into highly excited states, utilizing high-energy particles for enhanced energy applications. This study investigated the effects of DLTP on the electrochemical performance of bamboo charcoal (BC), utilizing bamboo shavings (BS) as the carbon source. The results indicated that the specific capacitance of BC varied under different atmospheric conditions, input voltages, and treatment durations, thereby achieving a maximum increase of 144 F/g. Furthermore, when combined with KOH activation, DLTP modification further enhanced the specific capacitance of BC to 237 F/g. The DLTP treatment enhanced the specific surface area and the types of functional groups in BC, thereby leading to a significant enhancement of its electrochemical properties.
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Two-dimensional (2D) heterostructure materials, incorporating the collective strengths and synergetic properties of individual building blocks, have attracted great interest as a novel paradigm in electrode materials science. The family of 2D transition metal carbides and nitrides (e.g., MXenes) has become an appealing platform for fabricating functional materials with strong application performance. Herein, a 2D LiFe0.3Mn0.7PO4 (LFMP)-on-MXene heterostructure composite is prepared through an electrostatic self-assembly procedure. The functional groups on the surface of MXenes possess highly electronegative properties that facilitate the incorporation of LFMPs into MXenes to construct heterostructure composites. The special heterostructure of nanosized-LiFe0.3Mn0.7PO4 and MXene provides rapid Li+ and electron transport in the cathodes. This LiFe0.3Mn0.7PO4-3.0 wt% MXene composite can exhibit an excellent rate capability of 98.3 mAh g-1 at 50C and a very stable cycling performance with a capacity retention of 94.3 % at 5C after 1000 cycles. Furthermore, NaFe0.3Mn0.7PO4-3.0 wt% MXene with stable cyclability can be obtained by an electrochemical conversion method with LiFe0.3Mn0.7PO4-3.0 wt% MXene. Ex-situ XRD suggests that LiFe0.3Mn0.7PO4-on-MXene achieves a highly reversible structural evolution with a solid solution phase transformation (LFMPâLixFe0.3Mn0.7PO4 (LxFMP), LxFMPâLFMP) and a two-phase reaction (LxFMPââFe0.3Mn0.7PO4 (FMP)). This work provides a new direction for the use of MXenes to fabricate 2D heterostructures for lithium-ion batteries.
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Organic-metal coordination materials with rich structural diversity are considered as promising electrode materials for rechargeable sodium-ion batteries. However, the electrochemical performance can be constrained by the limited number of active sites and structural instability under the discharge/charge process. Herein, organometallic polymer microspheres (Fe-PDA-220) with a unique d-π conjugated structure was designed and successfully constructed through a simple synchronous polymerization and coordination reactions. Polymerization of phenylenediamine was initiated by Fe3+ and Fe2+ ions generated synchronously during the polymerization integrated with poly-aminoquinone chains to form Fe-C12N8 active centers. Used as electrode materials for sodium-ion batteries, the distinctive Fe-C bond significantly boosts the structural stability, and the π-d conjugation system could facilitate electron transfer. A high reversible capacity of 345 mAh g-1 was delivered at 0.1 A g-1 and a capacity of 106 mAh g-1 was maintained even after discharged/charged at 1.0 A g-1 for 5000 cycles, outperforming most reported coordination materials. Spectroscopic and electronic analyses revealed that a two-electron reaction occurred per active unit, accompanied by the reversible redox evolution of the C=N groups and Fe ions during sodiation/desodiation. This work provides a promising and efficient strategy for boosting the electrochemical performance of organic electrode materials by the design of organometallic polymers.
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Rechargeable aluminum ion batteries (AIBs) have recently gained widespread research concern as energy storage technologies because of their advantages of being safe, economical, environmentally friendly, sustainable, and displaying high performance. Nevertheless, the intense Coulombic interactions between the Al3+ ions with high charge density and the lattice of the electrode body lead to poor cathode kinetics and limited cycle life in AIBs. This paper reviews the recent advances in the cathode design of AIBs to gain a comprehensive understanding of the opportunities and challenges presented by current AIBs. In addition, the advantages, limitations, and possible solutions of each cathode material are discussed. Finally, the future development prospect of the cathode materials is presented.
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The conceptualization and deployment of electrode materials for rechargeable sodium-ion batteries are key concerns for next-generation energy storage systems. In this contribution, the configuration stability of single-layer GeSiBi2 is systematically discussed based on first-principles calculations, and its potential as an anode material is further investigated. It is demonstrated that the phonon spectrum confirms the dynamic stability and the adsorption energy identifies a strong interaction between Na atoms and the substrate material. The electronic bands indicative of inherent metallicity contribute to the enhancement of electronic conductivity after Na adsorption. The multilayer adsorption of Na provides a theoretical capacity of 361.7 mAh/g, which is comparable to that of other representative two-dimensional anode materials. Moreover, the low diffusion barriers of 0.19 and 0.15 eV further guarantee the fast diffusion kinetics. These contributions signal that GeSiBi2 can be a compatible candidate for sodium-ion batteries anodes.
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SiOx-based anodes are of great promise for lithium-ion batteries due to their low working potential and high specific capacity. However, several issues involving large volume expansion during the lithiation process, low intrinsic conductivity, and unsatisfactory initial Coulombic efficiency (ICE) hinder their practical application. Here, an Fe-SiOx@C composite with significantly improved lithium-storage performance was successfully synthesized by combining Fe2+ modification with a carbon coating strategy. The results of both experiments and density functional theory calculations confirm that the Fe2+ modification not only effectively achieves uniform carbon coating but also weakens the bonding energy of the Si-O bond and boosts reversible lithiation/delithiation reactions, resulting in great improvement in the electrical conductivity, ICE, and reversible specific capacity of the as-obtained Fe-SiOx@C. Together with the coated carbon, the in situ-generated conductive Fe-based intermediates also ensure the electrical contact of active components, relieve the volume expansion, and maintain the structural integrity of the electrode during cycling. And the Fe-SiOx@C (x ≈ 1.5) electrode can deliver a high-rate capacity of 354 mA h g-1 at 2.0 A g-1 and long-term cycling stability (552.4 mA h g-1 at 0.5 A g-1 even after 500 cycles). The findings here provide a facile modification strategy to improve the electrochemical lithium-storage performance of SiOx-based anodes.
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A great challenge in the commercialization process of layered Ni-rich cathode material LiNixCoyMn1-x-yO2 (NCM, x ≥ 80%) for lithium-ion batteries is the surface instability, which is exacerbated by the increase in nickel content. The high surface alkalinity and unavoidable cathode/electrolyte interface side reactions result in significant decrease for the capacity of NCM material. Surface coating and doping are common and effective ways to improve the electrochemical performance of Ni-rich cathode material. In this study, an in situ reaction is induced on the surface of secondary particles of NCM material to construct a stable lithium sulfate coating, while achieving sulfur doping in the near surface region. The synergistic modification of lithium sulfate coating and lattice sulfur doping significantly reduced the content of harmful residual lithium compounds (RLCs) on the surface of NCM material, suppressed the side reactions between the cathode material surface and electrolyte and the degradation of surface structure of the NCM material, effectively improved the rate capability and cycling stability of the NCM material.
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Aluminum-ion batteries (AIBs), as electrochemical energy storage technologies, are advantageous because of their high theoretical specific capacity, lightweightness, zero pollution, safety, inexpensiveness, and abundant resources, which make them recent research hot spots. However, their electrolyte issues significantly limit their commercialization. The electrolyte choices for AIBs are significantly limited, and most of the available choices do not facilitate the three-electron-transfer reaction of Al3+/Al. Thus, this review presents an overview of recent advances in electrolytes, as well as modification strategies for AIBs, to clarify the limitations of existing AIB electrolytes and offer guidance for improving their performances. Furthermore, the advantages as well as limitations and possible solutions for each electrolyte are discussed, after which the future of AIB electrolytes is envisioned.
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Among the challenges related to rechargeable magnesium batteries (RMBs) still not resolved are positive electrode materials with sufficient charge storage and rate capability as well as stability and raw material resources. Out of the materials proposed and studied so far, vanadium oxides stand out for these requirements, but significant further improvements are expected and required. They will be based on new materials and an improved understanding of their mode of operation. This report provides a critical review focused on this material, which is embedded in a brief overview on the general subject. It starts with the main strategic ways to design layered vanadium oxides cathodes for RMBs. Taking these examples in more detail, the typical issues and challenges often missed in broader overviews and reviews are discussed. In particular, issues related to the electrochemistry of intercalation processes in layered vanadium oxides; advantageous strategies for the development of vanadium oxide composite cathodes; their mechanism in aqueous, "wet", and dry non-aqueous aprotic systems; and the possibility of co-intercalation processes involving protons and magnesium ions are considered. The perspectives for future development of vanadium oxide-based cathode materials are finally discussed and summarized.
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Chemically self-recharging zinc ion batteries (ZIBs), which are capable of auto-recharging in ambient air, are promising in self-powered battery systems. Nevertheless, the exclusive reliance on chemical energy from oxygen for ZIBs charging often would bring some obstacles in charging efficiency. Herein, we develop photo-assisted chemically self-recharging aqueous ZIBs with a heterojunction of MoS2/SnO2 cathode, which are favorable to enhancing both the charging and discharging efficiency as well as the chemical self-charging capabilities under illumination. The photo-assisted process promotes the electron transfer from MoS2/SnO2 to oxygen, accelerating the occurrence of the oxidation reaction during chemical self-charging. Furthermore, the electrons within the MoS2/SnO2 cathode exhibit a low transfer impedance under illumination, which is beneficial to reducing the migration barrier of Zn2+ within the cathode and thereby facilitating the uniform inserting of Zn2+ into MoS2/SnO2 cathode during discharging. This photo-assisted chemical self-recharging mechanism enables ZIBs to attain a maximum self-charging potential of 0.95 V within 3 hours, a considerable self-charging capacity of 202.5 mAh g-1 and excellent cycling performance in a self-charging mode. This work not only provides a route for optimizing chemical self-charging energy storage, but also broadens the potential application of aqueous ZIBs.
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Due to its many benefits, including high specific capacity, low voltage plateau, and plentiful supplies, silicon-based anode materials are a strong contender to replace graphite anodes. However, silicon has drawbacks such as poor electrical conductivity, abrupt volume changes during the discharge process, and continuous growth of the solid electrolyte interfacial (SEI) film during cycling, which would cause the electrode capacity to degrade quickly. Coating the silicon's exterior with carbon or metal oxide is a popular method to resolve the above-mentioned problems. In light of those above, the liquid-phase approach and electrostatic spinning technique were used in this work to create Si@MnO@CNFs bilayer-coated silicon-based anode materials. Because of the well-thought-out design, MnO and C bilaterally coat the silicon nanoparticles, significantly reducing their volume effect during cycling. Furthermore, manganese oxide has outstanding electrochemical kinetics and an excellent theoretical capacity. The carbon nanofibers' outermost layer increases the material's conductivity and stabilizes the composite material's structure, reducing the volume effect. After 1100 cycles at 2 A g-1, the composite anode material prepared in this work can still maintain a high capacity of 994.4 mAh g-1. This study offers an unusual combination of silicon and MnO that might set the way for the application of silicon-based composites in lithium-ion batteries.
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Functional modification of inorganic particles is an effective approach to tackle the issue of Li+ transport and the lithium dendrites formation in lithium-ion batteries (LIBs). In this study, PMIA/BiOCl composite separators are prepared by nonsolvent induce phase separation (NIPS) method using P-type semiconductor bismuth oxychloride (BiOCl) functionalized poly (m-phenylene isophthalamide) (PMIA) separators. Compared with the polypropylene (PP) separator, PMIA has superior thermal stability and the addition of BiOCl further enhances its flame retardancy. And the prepared PMIA/BiOCl separator presents improved porosity (66.47 %), enhanced electrolyte uptake rate (863 %) and higher ionic conductivity (0.49 mSâcm-1). Besides, the incorporation of BiOCl can anchor PF6- to the three-dimensional network skeleton of the PMIA/BiOCl separators, enabling the desolvation of Li+ and selectively facilitating Li+ transport (the Li+ transfer number is 0.79). Moreover, the uniform porous structure of the PMIA/BiOCl separators and the efficient transport of Li+ uniformly deposite Li+, and minimize the growth of lithium dendrites. Batteries assembled with PMIA/BiOCl separators have a discharge specific capacity of 124.4 mAhâg-1 and capacity retention of 96.7 % after 200 cycles at 0.2C. Therefore, this work provides an effective route in the design strategy of separators for LIBs.
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Silicon oxides (SiOx) have received extensive attention as an promising anode candidate for next-generation lithium-ion batteries (LIBs). However, their commerical applications have been seriously hindered by low conductivity, large volume expansion and unstable soild-electrolyte interface (SEI) layer, which result in low intial coulombic efficiency, poor rate performance and short cycling lifepan. In this work, we demonstrate a simple way to prepare a series of SiOx materials with lithium fluoride (LiF) modified by hydrothermal method and carbothermal modification. When the mass ratio of SiOx and LiF equals 1:0.15, the long-term cycling capacity retention can be greatly improve form 30.2% to 76.7% after 200 cycles. The result is primarily because the enhancement of electrons and Li+-ions transport and the stability of SEI layer due to LiF addition. However, excess LiF addition can hinder the diffusion of Li+-ions. This study presents the great potential of LiF modified on SiOx anode materials for LIBs.
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The cathode material of lithium-ion batteries (LIBs) is endowed with valuable metals, such as cobalt. The improper treatment of these batteries pollutes the environment and causes enormous resource waste. Therefore, the recovery of valuable metals from spent LIBs has attracted widespread attention. In this study, Co3O4 electrode materials were prepared by a simple homogeneous precipitation method and heat treatment using a leaching solution of spent LIBs-positive electrode material as the cobalt source. The crystal structure and morphology of the products were examined at different annealing temperatures, and their electrochemical performance was analyzed. The results show that low-temperature annealing contributes to grain refinement. The Co3O4 material prepared at 300°C annealing temperature has a rod-like structure with distinct pores and a specific surface area of 58.98 m2â g-1. Furthermore, electrochemical performance testing reveals that Co3O4 prepared at 300°C displays the best electrochemical performance as an electrode material, with a specific capacitance of 97.93 F g-1 and a cycle retention rate of 79.12% after 500 charge-discharge cycles. These findings demonstrate the feasibility of recycling valuable metal cobalt from spent LIBs cathode materials to produce Co3O4 materials for use as supercapacitor electrode materials, opening up new avenues for the recycling and utilisation of spent LIBs.