Trace Fluorinated Carbon dots driven Li-Garnet Solid-State Batteries.

Garnet solid-state electrolyte Li6.5La3Zr1.5Ta0.5O12 (LLZTO) holds significant promise. However, the practical utilization has been seriously impeded by the poor contact of Li|garnet and electron leakage. Herein, one new type garnet-based solid-state batteries is prososed with high-performance  through the disparity in interfacial energy, induced by the reaction between trace fluorinated carbon dots (FCDs) and Li. The work of adhesion of Li|garnet is increased by the acquired Li-FCD composite, which facilitates an intimate Li|garnet interface with the promoted uniform Li+ deposition, revealed by density functional theory (DFT) calculations. It is futher validated that a concentrated C-Li2O-LiF component at the Li|garnet interface is spontaneously constructed, due to the the significant disparity in interfacial energy between C-Li2O-LiF|LLZTO and C-Li2O-LiF|Li. Furthermore, The electron transport and Li dendrites penetration are effectively hindered by the formed Li2O and LiF. The Li-FCD|LLZTO|Li-FCD symmetrical cells demonstrate stable cycling performance for over 3000 hours at 0.3 mA cm-2 and 800 hours at 0.5 mA cm-2. Furthermore, the LFP|garnet|Li-FCD full cell exhibit remarkable cycling performance (91.6% capacity retention after 500 cycles at 1 C). Our research has revealed a novel approach to establish a dendrite-free Li|garnet interface, laying the groundwork for future advancements in garnet-based solid-state batteries.

Confined Element Distribution with Structure-driven Energy Coupling for Enhanced Prussian Blue Analogue Cathode.

The structural failure of Na2Mn[Fe(CN)6] could not be alleviated with traditional modification strategies through the adjustable composition property of Prussian blue analogues (PBAs), considering that the accumulation and release of stress derived from the MnN6 octahedrons are unilaterally restrained. Herein, a novel application of adjustable composition property, through constructing a coordination competition relationship between chelators and [Fe(CN)6]4- to directionally tune the enrichment of elements, is proposed to restrain structural degradation and induce unconventional energy coupling phenomenon. The non-uniform distribution of elements at the M1 site of PBAs (NFM-PB) is manipulated by the sequentially precipitated Ni, Fe, and Mn according to the Irving-William order. Electrochemically active Fe is operated to accompany Mn, and zero-strain Ni is modulated to enrich at the surface, synergistically mitigating with the enrichment and release of stress and then significantly improving the structural stability. Furthermore, unconventional energy coupling effect, a fusion of the electrochemical behavior between FeLS and MnHS, is triggered by the confined element distribution, leading to the enhanced electrochemical stability and anti-polarization ability. Consequently, the NFM-PB demonstrates superior rate performance and cycling stability. These findings further exploit potentialities of the adjustable composition property and provide new insights into the component design engineering for advanced PBAs.

Interfacial Mo-S-C Bond with High Reversibility for Advanced Alkali-Ion Capacitors: Strategies for High-Throughput Production.

The high-throughput scalable production of low-cost and high-performance electrode materials that work well under high power densities required in industrial application is full of challenges for the large-scale implementation of electrochemical technologies. Here, motivated by theoretical calculation that Mo-S-C heterojunction and sulfur vacancies can reduce the energy band gap, decrease the migration energy barrier, and improve the mechanical stability of MoS2 , the scalable preparation of inexpensive MoS2-x @CN is contrived by employing natural molybdenite as precursor, which is characteristic of high efficiency in synthesis process and energy conservation and the calculated costs are four orders of magnitude lower than MoS2 /C in previous work. More importantly, MoS2- x @CN electrode is endowed with impressive rate capability even at 5 A g-1 , and ultrastable cycling stability during almost 5000 cycles, which far outperform chemosynthesis MoS2 materials. Obtaining the full SIC cell assembled by MoS2- x @CN anode and carbon cathode, the energy/power output is high up to 265.3 W h kg-1 at 250 W kg-1 . These advantages indicate the huge potentials of the designed MoS2- x @CN and of mineral-based cost-effective and abundant resources as anode materials in high-performance AICs.

Chelate-Capped Nano-AgZn3 Dual Interphase Remodeling the Local Environment for Reversible Dendrite-Free Zinc Anode.

Rechargeable aqueous zinc-ion batteries (AZIBs) are among the most promising candidates for next-generation energy-storage devices. However, the large voltage polarisation and infamous dendrite growth hinder the practical application of AZIBs owing to their complex interfacial electrochemical environment. In this study, a hydrophobic zinc chelate-capped nano-silver (HZC-Ag) dual interphase is fabricated on the zinc anode surface using an emulsion-replacement strategy. The multifunctional HZC-Ag layer remodels the local electrochemical environment by facilitating the pre-enrichment and de-solvation of zinc ions and inducing homogeneous zinc nucleation, thus resulting in reversible dendrite-free zinc anodes. The zinc deposition mechanism on the HZC-Ag interphase is elucidated by density functional theory (DFT) calculations, dual-field simulations, and in situ synchrotron X-ray radiation imaging. The HZC-Ag@Zn anode exhibited superior dendrite-free zinc stripping/plating performance and an excellent lifespan of >2000 h with ultra-low polarisation of ≈17 mV at 0.5 mA cm-2 . Full cells coupled with a MnO2 cathode showed significant self-discharge inhibition, excellent rate performance, and improved cycling stability for >1000 cycles. Therefore, this multifunctional dual interphase may contribute to the design and development of dendrite-free anodes for high-performance aqueous metal-based batteries.

Interfacial Interaction of Multifunctional GQDs Reinforcing Polymer Electrolytes For All-Solid-State Li Battery.

Solid-state polymer electrolytes are highly anticipated for next generation lithium ion batteries with enhanced safety and energy density. However, a major disadvantage of polymer electrolytes is their low ionic conductivity at room temperature. In order to enhance the ionic conductivity, here, graphene quantum dots (GQDs) are employed to improve the poly (ethylene oxide) (PEO) based electrolyte. Owing to the increased amorphous areas of PEO and mobility of Li+ , GQDs modified composite polymer electrolytes achieved high ionic conductivity and favorable lithium ion transference numbers. Significantly, the abundant hydroxyl groups and amino groups originated from GQDs can serve as Lewis base sites and interact with lithium ions, thus promoting the dissociation of lithium salts and providing more ion pathways. Moreover, lithium dendrite is suppressed, associated with high transference number, enhanced mechanical properties and steady interface stability. It is further observed that all solid-state lithium batteries assembled with GQDs modified composite polymer electrolytes display excellent rate performance and cycling stability.

Improved Capacitive Energy Storage Nanocomposites at High Temperature Utilizing Ultralow Loading of Bimetallic MOF.

It is urgent to develop high-temperature dielectrics with high energy density and high energy efficiency for next-generation capacitor demands. Metal-organic frameworks (MOFs) have been widely used due to their structural diversity and functionally adaptable properties. Doping of metal nodes in MOFs is an effective strategy to change the band gap and band edge positions of the original MOFs, which helps to improve their ability to bind charges as traps. In this work, the incorporation of ultralow loading (<1.5 wt%) of novel bimetallic MOFs (ZIF 8-67) into the polyetherimide (PEI) polymer matrix is exhibited. With the addition of ZIF 8-67, the breakdown strength and energy storage capacity of ZIF 8-67/PEI nanocomposites are significantly improved, especially at high temperatures (200 °C). For example, the energy densitiy of the 0.5 wt% ZIF 8-67/PEI nanocomposite is up to 2.96 J cm-3 , with an efficiency (η) > 90% at 150 °C. At 200 °C, the discharge energy density of 0.25 wt% ZIF 8-67/PEI nanocomposites can still reach 1.84 J cm-3 with a η > 90%, which is nine times higher than that of pure PEI (0.21 J cm-3 ) under the same conditions, and it is the largest improvement compared with the previous reports.

Trapping Lithium Selenides with Evolving Heterogeneous Interfaces for High-Power Lithium-Ion Capacitors.

Transition metal selenides anodes with fast reaction kinetics and high theoretical specific capacity are expected to solve mismatched kinetics between cathode and anode in Li-ion capacitors. However, transition metal selenides face great challenges in the dissolution and shuttle problem of lithium selenides, which is the same as Li-Se batteries. Herein, inspired by the density functional theory calculations, heterogeneous can enhance the adsorption of Li2 Se relative to single component selenide electrodes, thus inhibiting the dissolution and shuttle effect of Li2 Se. A heterostructure material (denoted as CoSe2 /SnSe) with the ability to evolve continuously (CoSe2 /SnSe→Co/Sn→Co/Li13 Sn5 ) is successfully designed by employing CoSnO3 -MOF as a precursor. Impressively, CoSe2 /SnSe heterostructure material delivers the ultrahigh reversible specific capacity of 510 mAh g-1 after 1000 cycles at the high current density of 4 A g-1 . In situ XRD reveals the continuous evolution of the interface based on the transformation and alloying reactions during the charging and discharging process. Visualizations of in situ disassembly experiments demonstrate that the continuously evolving interface inhibits the shuttle of Li2 Se. This research proposes an innovative approach to inhibit the dissolution and shuttling of discharge intermediates (Li2 Se) of metal selenides, which is expected to be applied to metal sulfides or Li-Se and Li-S energy storage systems.

High Voltage Ga-Doped P2-Type Na2/3 Ni0.2 Mn0.8 O2 Cathode for Sodium-Ion Batteries.

Ni/Mn-based oxide cathode materials have drawn great attention due to their high discharge voltage and large capacity, but structural instability at high potential causes rapid capacity decay. How to moderate the capacity loss while maintaining the advantages of high discharge voltage remains challenging. Herein, the replacement of Mn ions by Ga ions is proposed in the P2-Na2/3 Ni0.2 Mn0.8 O2 cathode for improving their cycling performances without sacrificing the high discharge voltage. With the introduction of Ga ions, the relative movement between the transition metal ions is restricted and more Na ions are retained in the lattice at high voltage, leading to an enhanced redox activity of Ni ions, validated by ex situ synchrotron X-ray absorption spectrum and X-ray photoelectron spectroscopy. Additionally, the P2-O2 phase transition is replaced by a P2-OP4 phase transition with a smaller volume change, reducing the lattice strain in the c-axis direction, as detected by operando/ex situ X-ray diffraction. Consequently, the Na2/3 Ni0.21 Mn0.74 Ga0.05 O2 electrode exhibits a high discharge voltage close to that of the undoped materials, while increasing voltage retention from 79% to 93% after 50 cycles. This work offers a new avenue for designing high-energy density Ni/Mn-based oxide cathodes for sodium-ion batteries.

Electrochemically Engineering a Single-Crystal Nickel-Rich Layered Cathode.

Nickel-rich layered electrode material has been attracting significant attention owing to its high specific capacity as a cathode for lithium-ion batteries. Generally, the high-nickel ternary precursors obtained by traditional coprecipitation methods are micron-scale. In this work, the submicrometer single-crystal LiNi0.8Co0.1Mn0.1O2 (NCM) cathode is efficiently prepared by electrochemically anodic oxidation followed by a molten-salt-assisted reaction without the need of extreme alkaline environments and complex processes. More importantly, when prepared under optimal voltage (10 V), single-crystal NCM exhibits a moderate particle size (∼250 nm) and strong metal-oxygen bonds due to reasonable and balanced crystal nucleation/growth rate, which are conducive to greatly enhancing the Li+ diffusion kinetics and structure stability. Given that a good discharge capacity of 205.7 mAh g-1 at 0.1 C (1 C = 200 mAh g-1) and a superior capacity retention of 87.7% after 180 cycles at 1 C are obtained based on the NCM electrode, this strategy is effective and flexible for developing a submicrometer single-crystal nickel-rich layered cathode. Besides, it can be adopted to elevate the performance and utilization of nickel-rich cathode materials.

Advanced NASICON-Type Na4Fe3(PO4)2(P2O7) Cathode for High-Performance Na+/Li+ Batteries.

Na4Fe3(PO4)2(P2O7) (NFPP) is an attractive candidate for Na+ batteries (SIBs) and Li+ batteries (LIBs). However, the real implementation of NFPP has been critically restrained by the inferior intrinsic electronic conductivity. Herein, in situ carbon-coated mesoporous NFPP, obtained via freeze drying and heat treatment, demonstrates highly reversible insertion/extraction of Na+/Li+. Mechanically, the electronic transmission and structural stabilities of NFPP are significantly enhanced by the graphitized carbon coating layer. Chemically, the porous nanosized structure shortens Na+/Li+ diffusion paths and increases the contact area between the electrolyte and NFPP, ultimately rendering fast ion diffusion. Greatly, long-lasting cyclability (88.5% capacity retention for over 5000 cycles), decent thermal stability at 60 °C, and impressive electrochemical performances are demonstrated in LIBs. The insertion/extraction mechanisms of NFPP in both SIBs and LIBs are systematically investigated, confirming its small volume expansion and high reversibility. The superior electrochemical performances and the insertion/extraction mechanism investigation confirm the feasibility of utilizing NFPP as a cathode material for Na+/Li+ batteries.

Reconstructing Hydrogen Bond Network Enables High Voltage Aqueous Zinc-Ion Supercapacitors.

High-voltage aqueous rechargeable energy storage devices with safety and high specific energy are hopeful candidates for the future energy storage system. However, the electrochemical stability window of aqueous electrolytes is a great challenge. Herein, inspired by density functional theory (DFT), polyethylene glycol (PEG) can interact strongly with water molecules, effectively reconstructing the hydrogen bond network. In addition, N, N-dimethylformamide (DMF) can coordinate with Zn2+ , assisting in the rapid desolvation of Zn2+ and stable plating/stripping process. Remarkably, by introducing PEG400 and DMF as co-solvents into the electrolyte, a wide electrochemical window of 4.27 V can be achieved. The shift in spectra indicate the transformation in the number and strength of hydrogen bonds, verifying the reconstruction of hydrogen bond network, which can largely inhibit the activity of water molecule, according well with the molecular dynamics simulations (MD) and online electrochemical mass spectroscopy (OEMS). Based on this electrolyte, symmetric Zn cells survived up to 5000 h at 1 mA cm-2 , and high voltage aqueous zinc ion supercapacitors assembled with Zn anode and activated carbon cathode achieved 800 cycles at 0.1 A g-1 . This work provides a feasible approach for constructing high-voltage alkali metal ion supercapacitors through reconstruction strategy of hydrogen bond network.

Enabling Reversible Reaction by Uniform Distribution of Heterogeneous Intermediates on Defect-Rich SnSSe/C Layered Heterostructure for Ultralong-Cycling Sodium Storage.

2D layered Sn-based materials have attracted enormous attention due to their remarkable performance in sodium-ion batteries. Nevertheless, this promising candidate involves a complex Na+ -storage process with multistep conversion-alloying reactions, which induces the uneven dispersion of heterogeneous intermediate accompanied by severe agglomeration of metallic Sn0 , inescapably resulting in poor reaction reversibility with sluggish rate capability and inferior cyclic lifespan. Herein, a delicately layered heterostructure SnSSe/C consisting of defect-rich SnSSe and graphene is designed and successfully achieved via a facile hydrothermal process. The equal anionic substitution of Se in SnSSe crystal can trigger numerous defects, which can not only facilitate Na+ diffusion but also accelerate the nucleation process by inducing quantum-dot-level uniform distribution of heterogeneous intermediates, Na2 Se/Na2 S and Sn0 . Concurrently, in situ formed uniform Na2 Se/Na2 S grain boundaries confined by this unique layered heterostructure may effectively suppress the agglomeration of metallic Sn0 nanograins and boost the reversibility of conversion-alloying reaction. As a result, the SnSSe/C displays significant improvement in Na-storage performance, in terms of remarkable rate capability and ultralong cycling lifespan. This work, focusing on controlling intermediate distribution, provides an effective strategy to boost reaction reversibility, which can be wildly employed in conversion-based electrodes for energy storage regions.

A novel binding-induced DNAzyme motor triggered by survivin mRNA.

The accurate and sensitive detection of survivin mRNA is of great significance for cancer diagnosis and treatment. However, limited by the low-abundance mRNA in live cells, most strategies of survivin mRNA detection that were one-to-one signal-triggered model (one target triggered one signal) were inapplicable in practice. Here, we reported a binding-induced DNAzyme motor triggered by the survivin mRNA, which was a one-to-more signal-triggered model (one target triggered more signals), amplifying the detection signal and enhancing the sensitivity. The nanomotor is constructed by assembling several DNAzyme motor strands silenced by the blocker strands, and dozens of FAM-labeled substrate strands on a single gold nanoparticle (AuNP), forming three-dimensional DNA tracks. Through building the survivin mRNA bridge between the blocker and the DNAzyme motor strand, the binding-induced DNA nanomotor could be triggered by survivin mRNA. The operation of the DNAzyme motor was self-powered. And each walking step of the DNAzyme motor was fueled by DNAzyme-catalyzed substrate cleavage, along with the cleavage of the fluorescent molecule, resulting in autonomous and progressive walking along the AuNP-based tracks, and the fluorescence increase. The DNAzyme motor exhibited excellent sensitivity and remarkable specificity for survivin mRNA, providing the potential for cell image.

Structure and Interface Modification of Carbon Dots for Electrochemical Energy Application.

Carbon dots (CDs) as new nanomaterials have attracted much attention in recent years due to their unique characteristics. Notably, structure and interface modification (carbon core, edge, defects, and functional groups) of CDs have been considered as valid methods to regulate their properties, which contain electron transfer effect, electrochemical activity, fluorescence luminescent, and so on. Additionally, CDs with ultrasmall size, excellent dispersibility, high specific surface area, and abundant functional groups can guarantee positive and extraordinary effects in electrical energy storage and conversion. Therefore, CDs are used to couple with other materials by constructing a special interface structure to enhance their properties. Here, diverse structural and interfacial modifications of CDs with various heteroatoms and synergy effects are systematically analyzed. And not only several main syntheses of CDs-based composites (CDs/X) are summarized but also the merit and demerit of CDs/X in electrical energy storage are discussed. Finally, the applications of CDs/X in energy storage devices (supercapacitors, batteries) and electrocatalysts for practical applications are discussed. This review mainly provides a comprehensive summary and future prospect for synthesis, modification, and electrochemical applications of CDs.

Solid Solution Metal Chalcogenides for Sodium-Ion Batteries: The Recent Advances as Anodes.

The sodium-ion battery (SIB) has attracted ever growing attention as a promising alternative of the lithium-ion battery (LIB). Constructing appropriate anode materials is critical for speeding up the application of SIB. This review aims at guiding anode design from the material's perspective, and specifically focusing on solid solution metal chalcogenide anode. The sodium ion storage mechanisms of a solid solution metal chalcogenide anode is overviewed on basis of the elements it is composed of, and discusses how the solid solution character alters the electrochemical performances through diffusion and surface-controlled processes. In addition, by classifying solid solution metal chalcogenide as cation and anion, their recent applications are updated, and understanding the roles of guest elements in improving the electrochemical behaviors of a solid solution metal chalcogenide is carried out. After that, discussion of possible strategies to further optimize these anode materials in the future, flowing from crystal structure design to morphology control and finally to the intimacy improvement between conductive matrix and solid solution metal chalcogenide are also provided.

Carbon Dots Evoked Li Ion Dynamics for Solid State Battery.

Solid composite electrolyte-based Li battery is viewed as one of the most competitive system for the next generation batteries; however, it is still restricted by sluggish ion diffusion. Fast ion transport is a characteristic of the polyethylene oxide (PEO) amorphous phase, and the mobility of Li+ is restrained by the coordination interaction within PEO and Li+ . Herein, the design of applying functionalized carbon dots (CDs) with abundant surface features as fillers is proposed. High ionic conductivity is achieved in the CD-based composite electrolytes resulting from enhanced ion migration ability of polymer segments and mobility of Li+ . Specially, the optimum effect with nitrogen and sulfur co-doped carbon dots (NS-CD) is a consequence of strong interaction between edge-nitrogen/sulfur in NS-CD and Li+ . Solid-state nuclear magnetic resonance results confirm that more mobile Li+ is generated. Moreover, it is observed that lithium dendrite is suppressed compared to PEO electrolyte associated with reinforced mechanical properties and high transference number. The corresponding all-solid-state batteries, with the cathode of LiFePO4 or high voltage NCM523, exhibit long cycling life and excellent rate performances. It is a novel strategy to achieve high ionic conductivity composite electrolyte with uniform lithium deposition and provides a new direction to the mechanism of fast Li+ movement.

Presodiation Strategies for the Promotion of Sodium-Based Energy Storage Systems.

Nowadays sodium-based energy storage systems (Na-based ESSs) have been widely researched as it possesses the possibility to replace traditional energy storage media to become next generation energy storage system. However, due to the irreversible loss of sodium ions in the first cycle, development of Na-based ESSs is limited. Presodiation, as a strategy of adding excess sodium ions to the system in advance, accomplishes the enhancement of electrochemical performance. In this minireview, different presodiation strategies applied in sodium-based energy storage systems will be summarized in detail, their functions and corresponding mechanisms will be discussed as well. Furthermore, the current novel application of presodiation method in other aspects of Na-based ESSs will be mentioned additionally. At last, in the view of present research status of presodiation, issues that can be mitigated are put forward and guidelines are given on how to deliberate in-depth presodiation technology in the future, dedicating to promote the further development of Na-based ESSs.

Electrochemically Engineering Antimony Interspersed on Graphene toward Advanced Sodium-Storage Anodes.

Nanoengineering of metal anode materials shows great potential for energy storage with high capacity. Zero-dimensional nanoparticles are conducive to acquire remarkable electrochemical properties in sodium-ion batteries (SIBs) because of their enlarged surface active sites. However, it is still difficult to fulfill the requirements of practical applications in batteries owing to the deficiency of efficient and scalable preparation approaches of high-performance metal electrode materials. Herein, an electrochemical cathodic corrosion method is proposed for the tunable preparation of nanostructured antimony (Sb) by the introduction of a surfactant, which can efficiently avoid the agglomeration of Sb atom clusters generated from the Zintl compound and further stacking into bulk during the electrochemical process. Subsequently, graphene as the support and conductive matrix is uniformly interspersed by generating Sb nanoparticles (Sb/Gr). Moreover, the reversible crystalline-phase evolution of Sb ⇋ NaSb ⇋Na3Sb for Sb/Gr was studied by in situ X-ray diffraction (XRD). Benefiting from the interconnection of the conductive network, Sb/Gr anodes deliver a high capacity of 635.34 mAh g-1, a retained capacity of 507.2 mAh g-1 after 150 cycles at 0.1 C (1 C = 660 mAh g-1), and excellent rate performance with the capacities of 473.41 and 405.09 mAh g-1 at 2 and 5 C, respectively. The superior cycle stability with a capacity of 346.26 mAh g-1 is achieved after 500 cycles at 2 C. This electrochemical approach offers a new route toward developing metal anodes with designed nanostructures for high-performance SIBs.

Molecularly Compensated Pre-Metallation Strategy for Metal-Ion Batteries and Capacitors.

The use of a sacrificial cathode additive as a pre-metallation method could ensure adequate metal sources for advanced energy storage devices. However, this pre-metallation technique suffers from the precise regulation of decomposition potential of additive. Herein, a molecularly compensated pre-metallation (Li/Na/K) strategy has been achieved through Kolbe electrolysis, in which the electrochemical oxidation potential of a metal carboxylate is manipulated by the bonding energy of the oxygen-metal (O-M) moiety. The electron-donating effect of the substituent and the low charge density of the cation can dramatically weaken the O-M bond strength, further bringing out the reduced potential. Thus, sodium acetate exhibits a superior pre-sodiation feature for sodium-ion battery accompanied with a large irreversible specific capacity of 301.8 mAh g-1 , remarkably delivering 70.6 % enhanced capacity retention in comparison to the additive-free system after 100 cycles. This methodology has been extended to construct a high-performance lithium-ion battery and a lithium/sodium/potassium-ion capacitor.

Bi-Based Electrode Materials for Alkali Metal-Ion Batteries.

Alkali metal (Li, Na, K) ion batteries with high energy density are urgently required for large-scale energy storage applications while the lack of advanced anode materials restricts their development. Recently, Bi-based materials have been recognized as promising electrode candidates for alkali metal-ion batteries due to their high volumetric capacity and suitable operating potential. Herein, the latest progress of Bi-based electrode materials for alkali metal-ion batteries is summarized, mainly focusing on synthesis strategies, structural features, storage mechanisms, and the corresponding electrochemical performance. Particularly, the optimization of electrode-electrolyte interphase is also discussed. In addition, the remaining challenges and further perspectives of Bi-based electrode materials are outlined. This review aims to provide comprehensive knowledge of Bi-based materials and offer a guideline toward more applications in high-performance batteries.