Enabling Gradient-Structured Solid Electrolyte Interphase by a Hydrated Eutectic Electrolyte for High-Performance Zn Metal Batteries.

Aqueous Zn metal batteries are attracting tremendous interest as promising energy storage systems due to their intrinsic safety and cost-effectiveness. Nevertheless, the reversibility of Zn metal anodes (ZMAs) is hindered by water-induced parasitic reactions and dendrite growth. Herein, a novel hydrated eutectic electrolyte (HEE) consisting of Zn(BF4)2·xH2O and sulfolane (SL) is developed to prevent the side reactions and achieve the outstanding cyclability of ZMAs. The strong coordination between Zn2+ and SL triggers the eutectic feature, enabling the low-temperature availability of HEEs. The restriction of BF4 - hydrolysis in the eutectic system can realize favorable compatibility between Zn(BF4)2-based electrolyte and ZMAs. Besides, the newly-established solvation structure with the participation of SL, H2O, and BF4 -, can induce in situ formation of desirable SEI with gradient structure consisting of B,O-rich species, ZnS, and ZnF2, to offer satisfactory protection toward ZMAs. Consequently, the HEE allows the Zn||Zn symmetric cell to cycle over 1650 h at 2 mA cm-2 and 1 mA h cm-2. Moreover, the Zn||NH4V4O10 full batteries can deliver a prolonged lifespan for 1000 cycles with a high capacity retention of 83.4%. This work represents a feasible approach toward the elaborate design of advanced electrolyte systems for next-generation batteries.

Stable anode/separator interface enabled by graft modification of polypropylene separator via electron beam irradiation technique toward high-performance sodium metal batteries.

Sodium metal batteries (SMBs) are considered as strong alternatives to lithium-ion batteries (LIBs), due to the inherent merits of sodium metal anodes (SMAs) including low redox potential (-2.71 V vs. SHE), high theoretical capacity (1166 mAh g-1), and abundant resources. However, the uncontrollable Na dendrite growth has significantly impeded the practical deployment of SMBs. Separator modification has emerged as an effective strategy for substantially enhancing the performance of SMAs. Herein, for the first time, we present the successful grafting polyacrylic acid (PAA) onto polypropylene (PP) separators (denoted as PP-g-PAA) using highly efficient electron beam (EB) irradiation to improve the cyclability of SMAs. The polar carboxyl groups of PAA can facilitate the electrolyte wetting and provide ample mechanical strength to resist dendrite penetration. Consequently, the regulation of Na+ ion flux enables uniform Na+ deposition with dendrite-free morphology, facilitated by the favorable anode/separator interface. The PP-g-PAA separator significantly enhances the cyclability of fabricated cells. Notably, the lifespan of Na||Na symmetric cells can be extended up to 5519 h at 1 mA cm-2 and 1 mAh cm-2. The stable design of the anode/separator interface achieved through polyolefin separator modification presented in this study holds promise for the further advancement of next-generation advanced battery systems.

Electrolyte and Additive Engineering for Zn Anode Interfacial Regulation in Aqueous Zinc Batteries.

Aqueous Zn-metal batteries (AZMBs) have gained great interest due to their low cost, eco-friendliness, and inherent safety, which serve as a promising complement to the existing metal-based batteries, e.g., lithium-metal batteries and sodium-metal batteries. Although the utilization of aqueous electrolytes and Zn metal anode in AZMBs ensures their improved safety over other metal batteries meanwhile guaranteeing their decent energy density at the cell level, plenty of challenges involved with metallic Zn anode still await to be addressed, including dendrite growth, hydrogen evolution reaction, and zinc corrosion and passivation. In the past years, several attempts have been adopted to address these problems, among which engineering the aqueous electrolytes and additives is regarded as a facile and promising approach. In this review, a comprehensive summary of aqueous electrolytes and electrolyte additives will be given based on the recent literature, aiming at providing a fundamental understanding of the challenges associated with the metallic Zn anode in aqueous electrolytes, meanwhile offering a guideline for the electrolytes and additives engineering strategies toward stable AZMBs in the future.

A quasi-solid polymer electrolyte initiated by two-dimensional functional nanosheets for stable lithium metal batteries.

Lithium-metal batteries (LMBs) are expected to serve as next-generation energy storage systems due to their high theoretical energy density. However, their practical application is largely impeded due to the safety risks that arise from the uncontrollable Li dendrite growth and the high reactivity between high flammability liquid organic electrolytes and metallic lithium. Here, we report a highly safe quasi-solid gel polymer electrolyte (GPE) to achieve stable cycling of lithium metal with high coulombic efficiency, and it is prepared by in situ polymerization of 1,3-dioxolane (DOL) assisted by multi-functional H3Sb3P2O14 sheets. H3Sb3P2O14 acts as an initiator and a functional additive simultaneously that promotes the formation of a stable solid electrolyte interface (SEI) layer, thereby regulating the uniform deposition of Li and improving the Li plating/stripping efficiency. The obtained quasi-solid GPE exhibits high ionic conductivity and enhanced oxidative stability, favoring a stabilized electrode/electrolyte interface. Using the GPE, the electrochemical performance of the quasi-solid-state LMB with a LiFePO4 cathode and a lithium metal anode is significantly improved, delivering a discharge capacity of 125.7 mA h g-1 even after 1000 cycles. Therefore, the high reversibility and remarkable battery cyclability suggest that such a GPE is a promising choice of electrolyte for LMBs, while its facile preparation makes its large-scale application possible in the future.

Anion Storage of MXenes.

Recently, anion storage materials have gained significant attention owing to the widened cell voltage and additional anion storing capacity for a large energy density. MXenes are considered as the emerging anion storing materials owing to their sufficient interlayer spacing, rich surface chemistries, tunable structures, remarkable electrochemical properties, and mechanical integrity. Herein, a comprehensive review on the anion storage of MXenes covering their anion storage mechanism and state-of-the-art chemical strategies for the improved anion storage performances is reported. The recent progress of MXenes on aluminum ion batteries, metal halogen batteries, halogen ion batteries, and electrochemical electrode deionization is addressed. The scientific and technical challenges and the research direction into the anion storage of MXenes are also addressed and finally the authors' perspective on anion storage of MXenes is provided. Therefore, this review offers an insight into the rational design of MXenes for anion storage materials and the correlation of surface chemistries and structural modifications with anion storage properties for the applications into electrochemical energy storage and water purification.

Dendrites-Free Zn Metal Anodes Enabled by an Artificial Protective Layer Filled with 2D Anionic Nanosheets.

Metallic zinc (Zn) has been considered to be an ideal anode material for aqueous batteries, but is impeded by the growth of Zn dendrites and its side reactions with an aqueous electrolyte. Here, it is reported that an artificial protective layer filled with novel 2D Zn2+ adsorbed Sb3 P2 O14 3- (denoted as Zn-Sb3 P2 O14 ) nanosheets provide an effective route to mitigate the above challenging problems. The Zn-Sb3 P2 O14 protection layer not only avoids the direct contact with the aqueous electrolyte to suppress the side reactions but also allows for Zn-ions to pass through the protection layer rapidly. Moreover, the 2D Sb3 P2 O14 3- skeleton with negative charge also confines the 2D diffusion of Zn-ion along the lateral surface of Zn anode, resulting in a uniform electron-deposition. This unique protection layer not only enables dendrite-free Zn plating/stripping with an average Coulombic efficiency of 99.2% for 200 cycles, but also sustains the symmetric Zn||Zn cell over 1300 h at 1 mA cm-2 and 1 mAh cm-2 as well as for 450 h at 10 mA cm-2 and 10 mAh cm-2 . Such advantages bring high reversibility to full Zn batteries with MnO2 cathodes, which deliver a discharge capacity of 111.7 mAh g-1 after 1000 cycles.

Highly Stable Lithium/Sodium Metal Batteries with High Utilization Enabled by a Holey Two-Dimensional N-Doped TiNb2O7 Host.

Lithium/sodium metal batteries have attracted enormous attention as promising candidates for high-energy storage devices. However, their practical applications are impeded by the growth of dendrites upon Li/Na plating. Here, we report that holey 2D N-doped TiNb2O7 (N-TNO) nanosheets with high electroactive surface area and large amounts of lithiophilic/sodiophilic sites can effectively regulate Li/Na deposition as an interfacial layer, leading to an excellent cycling stability. The N-TNO interfacial layer enables the Li||Li symmetric cell to sustain stable electrodeposition over 1000 h as well as the Na||Na cell to stably cycle for 2400 h at 1 mA cm-2 and 3 mA h cm-2 with a depth of discharge as high as 50%. The full cells of the Li/Na anodes based on the N-TNO layer paired with the LiFePO4 and NaTi2(PO4)3 cathodes, respectively, show a very stable cycling over 1000 cycles at a negative-to-positive electrode capacity (N/P) ratio up to 3.

Bi Nanoparticles Embedded in 2D Carbon Nanosheets as an Interfacial Layer for Advanced Sodium Metal Anodes.

Sodium metal is regarded as one of the most prospective next-generation anodes material owing to its high theoretical capacity, low redox potential, low cost, and natural abundance. Its most notable problem is the dendrite growth during Na plating/striping, which causes not only the safety concern but also the generation of inactive Na. Here, it is demonstrated that 2D carbon nanosheets embedded by bismuth nanoparticles (NPs) (denoted as Bi⊂CNs) serve as a robust nucleation buffer layer to endow the sodium metal anodes (SMAs) with high Coulombic efficiencies (CEs) and dendrite-free deposition during long-term cycling. The embedded Bi nanoparticles significantly reduce the nucleation barrier through the "sodiophilic" Na-Bi alloy. Meanwhile, the carbon frameworks effectively circumvent the gradual failure of those Na-Bi nucleation sites. As a result, the metallic Na on the Bi⊂CNs nucleation layer is repeatedly plated/stripped for nearly 7700 h (1287 cycles) at 3 mA h cm-2 with an average CE of 99.92%. Moreover, the Na||Na symmetric cells with the Bi⊂CNs buffer layer are stably plated/stripped for 4000 h at 1 mA cm-2 and 1 mA h cm-2 . It is found that the cycling stability is closely related to the Na utilization of SMAs and current rate.

Stable Sodium Metal Anode Enabled by an Interface Protection Layer Rich in Organic Sulfide Salt.

Sodium (Na) metal is considered as a promising anode candidate for large-scale energy storage systems because of its high theoretical capacity and low electrochemical redox potential. However, Na anode suffers from a few challenges, such as the dendrite growth and severe parasitic reactions with electrolytes, which greatly hinder its practical applications. In this work, we demonstrate that an organosulfur compound additive (tetramethylthiuram disulfide) provides a facile and promising approach to overcome the above challenges in carbonate-based electrolytes. This unique organosulfur additive can in situ form a stable interfacial protection layer rich in organic sulfide salts on the sodium metal surface during cycling, leading to a stable stripping/plating cycling. Additionally, a cycling Coulombic efficiency of 94.25% is achieved, and the full battery using Prussian Blue as a cathode delivers a reversible capacity of 86.2 mAh g-1 with a capacity retention of 80% after 600 cycles at 4 C.

Core-Shell C@Sb Nanoparticles as a Nucleation Layer for High-Performance Sodium Metal Anodes.

Sodium metal anode (SMA) is one of the most favored choices for the next-generation rechargeable battery technologies owing to its low cost and natural abundance. However, the poor reversibility resulted from dendrite growth and formation of unstable solid electrolyte interphase has significantly hindered the practical application of SMAs. Herein, we report that a nucleation buffer layer comprising elaborately designed core-shell C@Sb nanoparticles (NPs) enables the homogeneous electrochemical deposition of sodium metal for long-term cycling. These C@Sb NPs can increase active sites for initial sodium nucleation through Sb-Na alloy cores and keep these cores stable through carbon shells. The assembled cells with this nucleation layer can deliver continuously repeated sodium plating/stripping cycles for nearly 6000 h at a high areal capacity of 4 mA h cm-2 with an average Coulombic efficiency 99.7%. This ingenious structure design of alloy-based nucleation agent opens up a promising avenue to stabilize sodium metal with targeted properties.

Dendrite-Free Sodium Metal Anodes Enabled by a Sodium Benzenedithiolate-Rich Protection Layer.

Sodium metal is an ideal anode material for metal rechargeable batteries, owing to its high theoretical capacity (1166 mAh g-1 ), low cost, and earth-abundance. However, the dendritic growth upon Na plating, stemming from unstable solid electrolyte interphase (SEI) film, is a major and most notable problem. Here, a sodium benzenedithiolate (PhS2 Na2 )-rich protection layer is synthesized in situ on sodium by a facile method that effectively prevents dendrite growth in the carbonate electrolyte, leading to stabilized sodium metal electrodeposition for 400 cycles (800 h) of repeated plating/stripping at a current density of 1 mA cm-2 . The organic salt, PhS2 Na2 , is found to be a critical component in the protection layer. This finding opens up a new and promising avenue, based on organic sodium slats, to stabilize sodium metals with a protection layer.

Graphene-Encapsulated CuP2: A Promising Anode Material with High Reversible Capacity and Superior Rate-Performance for Sodium-Ion Batteries.

Metal polyphosphides are regarded as the ideal anode candidates for sodium storage because of their high theoretical capacity, reasonable potential, and abundant resource alternative. However, most of them suffer from irreversibility problems, as reflected by their low reversible capacity, inferior Coulombic efficiency (CE), low rate capability, and poor cycling stability. In this work, we systematically compare the electrochemical behavior of a variety of polyphosphides bulks, discovering that the CuP2 bulks have higher initial reversible capacity (416 mAh g-1 at 0.1 A g-1) and CE (74%) compared to the FeP2, CoP3, and NiP2 bulks, which is related to the unique crystal structure of CuP2. The CuP2 electrode is optimized by the rational design of encapsulating CuP2 nanoparticles into three-dimensional graphene networks (CuP2@GNs), leading to excellent electrochemical performance. In the carbonate electrolyte, the CuP2@GNs electrode can deliver the reversible capacities of up to 804, 736, 685, 621, and 508 mAh g-1 at 0.1, 0.5, 1, 2, and 5 A g-1, respectively, along with a first CE of 66%. The reversible capacity can be up to 737 mAh g-1 at 0.1 A g-1 with a first CE of 83% in the ether electrolyte. These excellent performance demonstrates that CuP2@GNs could be a promising anode material for sodium-ion batteries.

Decorating TiO2 Nanowires with BaTiO3 Nanoparticles: A New Approach Leading to Substantially Enhanced Energy Storage Capability of High-k Polymer Nanocomposites.

The urgent demand of high energy density and high power density devices has triggered significant interest in high dielectric constant (high-k) flexible nanocomposites comprising dielectric polymer and high-k inorganic nanofiller. However, the large electrical mismatch between polymer and nanofiller usually leads to earlier electric failure of the nanocomposites, resulting in an undesirable decrease of electrical energy storage capability. A few studies show that the introduction of moderate-k shell onto a high-k nanofiller surface can decrease the dielectric constant mismatch, and thus, the corresponding nanocomposites can withstand high electric field. Unfortunately, the low apparent dielectric enhancement of the nanocomposites and high electrical conductivity mismatch between matrix and nanofiller still result in low energy density and low efficiency. In this study, it is demonstrated that encapsulating moderate-k nanofiller with high-k but low electrical conductivity shell is effective to significantly enhance the energy storage capability of dielectric polymer nanocomposites. Specifically, using BaTiO3 nanoparticles encapsulated TiO2 (BaTiO3@TiO2) core-shell nanowires as filler, the corresponding poly(vinylidene fluoride-co-hexafluoropylene) nanocomposites exhibit superior energy storage capability in comparison with the nanocomposites filled by either BaTiO3 or TiO2 nanowires. The nanocomposite film with 5 wt % BaTiO3@TiO2 nanowires possesses an ultrahigh discharged energy density of 9.95 J cm-3 at 500 MV m-1, much higher than that of commercial biaxial-oriented polypropylene (BOPP) (3.56 J cm-3 at 600 MV m-1). This new strategy and corresponding results presented here provide new insights into the design of dielectric polymer nanocomposites with high electrical energy storage capability.

Substantial enhancement of energy storage capability in polymer nanocomposites by encapsulation of BaTiO3 NWs with variable shell thickness.

Dielectric polymer nanocomposites have received keen interest due to their potential application in energy storage. Nevertheless, the large contrast in dielectric constant between the polymer and nanofillers usually results in a significant decrease of breakdown strength of the nanocomposites, which is unfavorable for enhancing energy storage capability. Herein, BaTiO3 nanowires (NWs) encapsulated by TiO2 shells of variable thickness were utilized to fabricate dielectric polymer nanocomposites. Compared with nanocomposites with bare BaTiO3 NWs, significantly enhanced energy storage capability was achieved for nanocomposites with TiO2 encapsulated BaTiO3 NWs. For instance, an ultrahigh energy density of 9.53 J cm-3 at 440 MV m-1 could be obtained for nanocomposites comprising core-shell structured nanowires, much higher than that of nanocomposites with 5 wt% raw ones (5.60 J cm-3 at 360 MV m-1). The discharged energy density of the proposed nanocomposites with 5 wt% mTiO2@BaTiO3-1 NWs at 440 MV m-1 seems to rival or exceed those of some previously reported nanocomposites (mostly comprising core-shell structured nanofillers). More notably, this study revealed that the energy storage capability of the nanocomposites can be tailored by the TiO2 shell thickness. Finite element simulations were employed to analyze the electric field distribution in the nanocomposites. The enhanced energy storage capability should be mainly attributed to the smoother gradient of dielectric constant between the nanofillers and polymer matrix, which alleviated the electric field concentration and leakage current in the polymer matrix. The methods and results herein offer a feasible approach to construct high-energy-density polymer nanocomposites with core-shell structured nanowires.

Bio-Inspired Fluoro-polydopamine Meets Barium Titanate Nanowires: A Perfect Combination to Enhance Energy Storage Capability of Polymer Nanocomposites.

Rapid evolution of energy storage devices expedites the development of high-energy-density materials with excellent flexibility and easy processing. The search for such materials has triggered the development of high-dielectric-constant (high-k) polymer nanocomposites. However, the enhancement of k usually suffers from sharp reduction of breakdown strength, which is detrimental to substantial increase of energy storage capability. Herein, the combination of bio-inspired fluoro-polydopamine functionalized BaTiO3 nanowires (NWs) and a fluoropolymer matrix offers a new thought to prepare polymer nanocomposites. The elaborate functionalization of BaTiO3 NWs with fluoro-polydopamine has guaranteed both the increase of k and the maintenance of breakdown strength, resulting in significantly enhanced energy storage capability. The nanocomposite with 5 vol % functionalized BaTiO3 NWs discharges an ultrahigh energy density of 12.87 J cm-3 at a relatively low electric field of 480 MV m-1, more than three and a half times that of biaxial-oriented polypropylene (BOPP, 3.56 J cm-3 at 600 MV m-1). This superior energy storage capability seems to rival or exceed some reported advanced nanoceramics-based materials at 500 MV m-1. This new strategy permits insights into the construction of polymer nanocomposites with high energy storage capability.

Mussel-inspired Fluoro-Polydopamine Functionalization of Titanium Dioxide Nanowires for Polymer Nanocomposites with Significantly Enhanced Energy Storage Capability.

High-dielectric-constant polymer nanocomposites are demonstrated to show great promise as energy storage materials. However, the large electrical mismatch and incompatibility between nanofillers and polymer matrix usually give rise to significantly reduced breakdown strength and weak energy storage capability. Therefore, rational selection and elaborate functionalization of nanofillers to optimize the performance of polymer nanocomposites are vital. Herein, inspired by adhesive proteins in mussels, a facile modification by fluoro-polydopamine is employed to reinforce the compatibility of TiO2 nanowires in the fluoropolymer matrix. The loading of 2.5 vol % f-DOPA@TiO2 NWs leads to an ultrahigh discharged energy density of 11.48 J cm-3 at 530 MV m-1, more than three times of commercial biaxial-oriented polypropylene (BOPP, 3.56 J cm-3 at 600 MV m-1). A gratifying high energy density of 9.12 J cm-3 has also been obtained with nanofiller loading as high as 15 vol % at 360 MV m-1, which is nearly double to that of pure P(VDF-HFP) (4.76 J cm-3 at 360 MV m-1). This splendid energy storage capability seems to rival or exceed most of previously reported nano-TiO2 based nanocomposites. The methods presented here provide deep insights into the design of polymer nanocomposites for energy storage applications.

Tailoring Dielectric Properties and Energy Density of Ferroelectric Polymer Nanocomposites by High-k Nanowires.

High dielectric constant (k) polymer nanocomposites have shown great potential in dielectric and energy storage applications in the past few decades. The introduction of high-k nanomaterials into ferroelectric polymers has proven to be a promising strategy for the fabrication of high-k nanocomposites. One-dimensional large-aspect-ratio nanowires exhibit superiority in enhancing k values and energy density of polymer nanocomposites in comparison to their spherical counterparts. However, the impact of their intrinsic properties on the dielectric properties of polymer nanocomposites has been seldom investigated. Herein, four kinds of nanowires (Na2Ti3O7, TiO2, BaTiO3, and SrTiO3) with different inherent characteristics are elaborately selected to fabricate high-k ferroelectric polymer nanocomposites. Dopamine functionalization facilitates the excellent dispersion of these nanowires in the ferroelectric polymer matrix because of the strong polymer/nanowire interfacial adhesion. A thorough comparative study on the dielectric properties and energy storage capability of the nanowires-based nanocomposites has been presented. The results reveal that, among the four types of nanowires, BaTiO3 NWs show the best potential in improving the energy storage capability of the proposed nanocomposites, resulting from the most signficant increase of k while retaining the rather low dielectric loss and leakage current.

A facile fluorescence method for versatile biomolecular detection based on pristine α-Fe2O3 nanoparticle-induced fluorescence quenching.

This work investigated the interactions of α-Fe2O3 nanoparticles (NPs) with different structural nucleic acids and their fluorescence quenching ability towards fluorophore-labelled nucleic acid probes. Different from bulk α-Fe2O3 samples, nanoscale α-Fe2O3 particles exhibit the unique properties of strong adsorption and fluorescence quenching to fluorophore-labelled single-stranded DNA (ssDNA) probes. Based on these findings, a facile fluorescence method was developed for versatile quantification of nucleic acids. The size scale of NPs makes a significant impact on this sensing platform. Better selectivity was given by bigger NP (50-100 nm)-based nucleic acid-sensing platform compared with smaller NP (30 nm)-based one. In the 50-100 nm α-Fe2O3 NP-based sensing platform, single nucleotide mismatch or single base-pair mismatch can even be effectively discriminated. The targets of micro-RNA (miRNA), ssDNA and double-stranded DNA (dsDNA) are sensitively detected with detection limits of 0.8 nM, 1.1 nM and 0.64 nM (S/N=3), respectively. Significantly, α-Fe2O3 NPs possess different affinities towards ssDNA probes with different lengths, and can be used as a universal quencher for ssDNA probes labelled with different fluorescent dyes. On the basis of these properties, the pristine α-Fe2O3 NPs hold the potential to be widely utilized in the development of novel biosensors with signal amplification or simultaneous multiple target detection strategies.

A barium based coordination polymer for the activity assay of deoxyribonuclease I.

A new coordination polymer which shows an unusual 2D inorganic connectivity was constructed. This compound exhibits distinct fluorescence quenching ability to the dye-labeled single-stranded DNA probes with different lengths, based on which an analytical method was developed for the activity assay of deoxyribonuclease I.

Applications of porous organic frameworks (POFs) in detection of nucleic acid and exonuclease I activity.

As a two-dimensional (2D) ordered porous organic framework (POF), PAF-6 is demonstrated to have an extraordinarily high fluorescence quenching ability to dye-labeled single-stranded DNA (ssDNA). Based on its different affinities to ssDNA and double-stranded DNA (dsDNA), and to ssDNAs with different lengths, PAF-6 is firstly utilized as a simple, cost-efficient, sensitive and selective sensing platform for sequence-specific detection of DNA and activity analysis of exonuclease I (Exo I). In these two systems, the sensing approach is accomplished by simply mixing the dye-labeled ssDNA probe with the targets and PAF-6. The targets of DNA and Exo I are specifically and sensitively detected with detection limits of 0.6 nM and 0.03 U mL-1 (S/N = 3), respectively, by using PAF-6 as a fluorescence quencher of the dye-labeled ssDNA probe. The results of this study suggest that PAF-6 can be developed as an excellent platform for the detection of nucleic acid and nuclease activity. In addition, PAF-6 exhibits a remarkable ability to protect ssDNA probe from enzymatic digestion, which may greatly extend the applications of the proposed ssDNA probe/PAF-6 sensing system to bioanalysis and biomedicine.