Sb-Doped Biphasic P2/O3-Type Mn-Rich Layered Oxide Cathode Material for High-Performance Sodium-Ion Batteries.

Mn-rich P2-type layered oxide cathode materials suffer from severe capacity loss caused by detrimental phase transition and transition metal dissolution, making their implementation difficult in large-scale sodium-ion battery applications. Herein, we introduced a high-valent Sb5+ substitution, leading to a biphasic P2/O3 cathode that suppresses the P2-O2 phase transformation in the high-voltage condition attributed to the stronger Sb-O covalency that introduces extra electrons to the O atom, reducing oxygen loss from the lattices and improving structural stability, as confirmed by first-principle calculations. Besides, the enhanced Na+ diffusion kinetics and thermodynamics in the modified sample are associated with the enlarged lattice parameters. As a result, the proposed cathode delivers a discharge capacity of 142.6 mAh g-1 at 0.1C between 1.5 and 4.3 V and excellent performance at a high mass loading of 8 mg cm3 with a specific capacity of 131 mAh g-1 at 0.2C. Furthermore, it also possesses remarkable rate capability (90.3 mAh g-1 at 5C), specifying its practicality in high-energy-density sodium-ion batteries. Hence, this work provides insights into incorporating high-valent dopants for high-performance Mn-rich cathodes.

Achieving highly stable sodium metal batteries with self-adapting and high-ionic-mobility ceramic fiber membranes.

Tough issues like sodium (Na) dendrite growth and poor anode reversibility hinder the practical application of sodium metal batteries (SMBs) with moderate liquid electrolytes. To settle these problems, using a smart self-adapting Al2SiO5 ceramic fiber (CF) membrane is demonstrated to enable homogeneous Na depositions and inhibit the dendritic growth. This inorganic membrane itself has superb thermal stability, high ionic mobility (Na+ transference number: 0.65) and electrolyte wettability over traditional glass fiber (GF) or polymeric ones, guaranteeing the low voltage polarization (14 mV) and long-cyclic lifetime (over 600 h) in symmetric cells testing. Notably, aluminous components in CF membranes would interact with F-based molecules in the electrolyte phase, thereby releasing some Al3+ species that can be electrochemically deposited onto the anodic interface. The packed (+)Na3V2(PO4)3|CF|Na(-) full SMBs exhibit far superior cyclic stability (capacity retention over 78.7 % after 600 cycles at 1C) than other counterparts. The in-situ detection/postmortem analysis reveal that Al/F-based inorganics formed in as-built SEI layers play a vital role in Na metal anode protection. This work may provide a viable strategy to overcome the constraints of high-energy SMBs in practical applications.

ZnO Additive Boosts Charging Speed and Cycling Stability of Electrolytic Zn-Mn Batteries.

Electrolytic aqueous zinc-manganese (Zn-Mn) batteries have the advantage of high discharge voltage and high capacity due to two-electron reactions. However, the pitfall of electrolytic Zn-Mn batteries is the sluggish deposition reaction kinetics of manganese oxide during the charge process and short cycle life. We show that, incorporating ZnO electrolyte additive can form a neutral and highly viscous gel-like electrolyte and render a new form of electrolytic Zn-Mn batteries with significantly improved charging capabilities. Specifically, the ZnO gel-like electrolyte activates the zinc sulfate hydroxide hydrate assisted Mn2+ deposition reaction and induces phase and structure change of the deposited manganese oxide (Zn2Mn3O8·H2O nanorods array), resulting in a significant enhancement of the charge capability and discharge efficiency. The charge capacity increases to 2.5 mAh cm-2 after 1 h constant-voltage charging at 2.0 V vs. Zn/Zn2+, and the capacity can retain for up to 2000 cycles with negligible attenuation. This research lays the foundation for the advancement of electrolytic Zn-Mn batteries with enhanced charging capability.

One-Step Pyrolysis Construction of Bimetallic Atom-Cluster Sites for Boosting Bifunctional Catalytic Activity in Zn-Air Batteries.

Due to their unique advantages, single atoms and clusters of transition metals are expected to achieve a breakthrough in catalytic activity, but large-scale production of active materials remains a challenge. In this work, a simple solvent-free one-step annealing method is developed and applied to construct diatomic and cluster active sites in activated carbon by utilizing the strong anchoring ability of phenanthroline to metal ions, which can be scaled for mass productions. Benefiting from the synergy between the different metals, the obtained sub-nano-bimetallic atom-cluster catalysts (FeNiAC -NC) exhibit high oxygen reduction reactions (ORR) activity (E1/2 = 0.936 V vs. RHE) and a small ORR/oxygen evolution reaction (OER) potential gap of only 0.594 V. An in-house pouch Zn-air battery is assembled using an FeNiAC -NC catalyst, which demonstrates a stability of 1000 h, outperforming previous reports. The existence of clusters and their effects on catalytic activity is analyzed by density functional theory calculations to reveal the chemistry of nano-bimetallic atom-cluster catalysts.

Amorphous Vanadium Oxides with Dual ion Storage Mechanism for High-Performance Aqueous Zinc ion Batteries.

Owing to the extremely limited structural deformation caused by the introduction of guest ions that their rigid structure can sustain, crystalline materials typically fail owing to structural collapse when utilized as electrode materials. Amorphous materials, conversely, are more resistant to volume expansion during dynamic ion transport and can introduce a lot of defects as active sites. Here, The amorphous polyaniline-coated/intercalated V2O5·nH2O (PVOH) nanowires are prepared by in situ chemical oxidation combined with self-assembly strategy, which exhibited impressive electrochemical properties because of its short-range ordered crystal structure, oxygen vacancy/defect-rich, improved electronic channels, and ionic channels. Through in situ techniques, the energy storage mechanism of its Zn2+/H+ co-storage is investigated and elucidated. Additionally, this work provides new insights and perspectives for the investigation and application of amorphous cathodes for aqueous zinc ion batteries.

Structural regulation of asphalt-based hard carbon microcrystals based on liquid-phase crosslinking to enhance sodium storage.

Air-oxidation is an effective strategy to obtain promising carbon materials from asphalt for sodium-ion batteries. However, this method would generate a vast amount of gaseous pollutant, which pose challenges for recycling. Herein, a simple, cost-effective and environmentally friendly liquid-phase oxidation method is proposed. The oxygen-containing functional groups (-NO2) are introduced into asphalt, which effectively prevents the melting of asphalt and rearrangement of carbon layers during subsequent carbonization process. As a result, a carbon material with notable disorder degree, large interlayer spacing and abundant closed pores, is prepared. The as-prepared product demonstrates an impressive initial Coulombic efficiency of 88.3 % and an enhanced specific capacity of 317.0 mA h g-1, which is 2.6 times that of the pristine product. Moreover, when assembled with a Na3.32Fe2.34(P2O7)2 cathode, the full-cell delivers a high reversible capacity of 271.7 mA h g-1 at 30 mA g-1 with superb cycle life. This study offers a novel oxidation strategy and provides a solution for producing highly disordered carbon anodes from soft carbon precursors.

Continuous Amorphous Metal-Organic Frameworks Layer Boosts the Performance of Metal Anodes.

Employing metal anodes can greatly increase the volumetric/gravimetric energy density versus a conventional ion-insertion anode. However, metal anodes are plagued by dendrites, corrosion, and interfacial side reaction issues. Herein, a continuous and flexible amorphous MOF layer was successfully synthesized and used as a protective layer on metal anodes. Compared with the crystalline MOF layer, the continuous amorphous MOF layer can inhibit dendrite growth at the grain boundary and eliminate ion migration near the grain boundary, showing high interfacial adhesion and a large ion migration number (tZn2+ = 0.75). In addition, the continuous amorphous MOF layer can effectively solve several key challenges, e.g., corrosion of the zinc anode, hydrogen evolution reaction, and dendrite growth on the zinc surface. The prepared Zn anode with the continuous amorphous MOF (A-MOF) layer exhibited an ultralong cycling life (around one year, more than 7900 h) and a low overpotential (<40 mV), which is 12 times higher than that of the crystalline MOF protective layer. Even at 10 mA cm-2, it still showed high stability for more than 5500 cycles (1200 h). The enhanced performance is realized for full cells paired with a MnO2 cathode. In addition, a flexible symmetrical battery with the Zn@A-ZIF-8 anode exhibited good cyclability under different bending angles (0°, 90°, and 180°). More importantly, various metal substrates were successfully coated with compact A-ZIF-8. The A-ZIF-8 layer can obviously improve the stability of other metal anodes, including those of Mg and Al. These results not only demonstrate the high potential of amorphous MOF-decorated Zn anodes for AZIBs but also propose a type of protective layer for metal anodes.

Thickness-Controlled Synthesis of Compact and Uniform MOF Protective Layer for Zinc Anode to Achieve 85% Zinc Utilization.

Zinc anode-based aqueous batteries have attracted considerable interest for large-scale energy storage and wearable devices. Unfortunately, the formation of Zn dendrite, parasitic hydrogen evolution reaction (HER), and irreversible by-products, seriously restrict their practical applications. Herein, a series of compact and uniform metal-organic frameworks (MOFs) films with precisely controlled thickness (150-600 nm) are constructed by a pre-oxide gas deposition (POGD) method on Zn foil. Under the protection of MOF layer with optimum thickness, the corrosion of zinc, the side reaction of hydrogen evolution, and the growth of dendrites on the zinc surface are suppressed. The symmetric cell based on Zn@ZIF-8 anode exhibits exceptional cyclicality for over 1100 h with low voltage hysteresis of≈38 mV at 1 mA cm-2 . Even at current densities of 50 mA cm-2 with an area capacity of 50 mAh cm-2 (85% Zn utilization), the electrode can keep cycling for >100 h. Besides, this Zn@ZIF-8 anode also delivers a high average CE of 99.4% at 1 mA cm-2 . Moreover, a rechargeable Zn ion battery is fabricated based on the Zn@ZIF-8 anode and MnO2 cathode, which presents an exceptionally long lifespan with no capacity attenuation for 1000 cycles.

A Ternary Composite with Medium Adsorption Confirms Good Reversibility of Li-Se Batteries.

For Li-Se batteries, cathode using carbonaceous hosts to accommodate Se performed modestly, whereas those applying metallic compounds with stronger chemical adsorption exhibited even more rapid capacity decay, the intrinsic reasons for which are still not clear. Herein, it is found that Se tends to precipitate on the surface of the electrode during cycling, and the precipitation speed depends on the polarization degree of the host. A further enhanced adsorption does not certainly generate better electrochemical activity, since hosts with overhigh adsorption ability are hard to desorb polyselenides, leading to catalyst passivation and rapid capacity decay. These findings encourage us to design a ternary anatase/rutile/titanium nitride (aTiO2 /rTiO2 /TiN@C) composite host, integrating good adsorption of TiO2 and rapid electron transport ability of TiN, and introducing rutile to weaken overall adsorption. The aTiO2 /rTiO2 /TiN@C composite with medium adsorption not only avoids rapid loss of active substances in electrolyte but also slows down the precipitation speed of Se. As a result, the aTiO2 /rTiO2 /TiN@C/Se electrode delivered good rate capability(154 mA h g-1 at 20 C) and good cycling stability(a low decay of 0.024% per cycle within 500 cycles at 2 C).

N doped FeP nanospheres decorated carbon matrix as an efficient electrocatalyst for durable lithium-sulfur batteries.

Rational design and synthesis of multifunctional electrocatalysts with high electrochemical activity and low cost are significantly important for new-generation lithium-sulfur (Li-S) batteries. Herein, N-doped FeP nanospheres decorated N doped carbon matrix is successfully synthesized by facile one-pot pyrolysis and in-situ phosphorization technique to mitigate the conversion kinetics and suppress the shuttle effect. The large specific surface area with mesopores can incorporate up to 81.5% sulfur, with the conductive carbon and nitrogen co-matrix providing Li+/e- passage and fastening the redox kinetics. The remarkable adsorption properties and the electrocatalytic activity through physical confinement and chemical immobilization is thoroughly verified. Consequently, the FeP/CN@S deliver a high reversible capacity of 1183 mAh g-1 at 0.1C compared to Co/P/CN@S (961 mAh g-1); whereas, at 1C, a negligible decay rate of 0.04% is observed for 1000 cycles, possessing outstanding cycling stability and rate capability. Hence, the cost-effective in-situ phosphorization strategy to synthesize FeP/CN@S as an efficient nanoreactor is constructive to be applied in Li-S batteries.

Electrostatically directed assembly of two-dimensional ultrathin Co2Ni-MOF/Ti3C2Tx nanosheets for electrocatalytic oxygen evolution.

Hydrogen production from water electrolysis is severely restricted by the poor reaction kinetics of oxygen evolution reaction (OER). In this work, a series of two-dimensional (2D) composites MOF/Ti3C2Tx (the MXene phase) were fabricated by electrostatically directed assembly and used as catalysts for OER. The obtained composite materials exhibit enhanced electrocatalytic properties, thanks to the ultrathin 2D/2D heterostructure with abundant active sites in Co2Ni-MOF and the high electronic conductivity of Ti3C2Tx. Among all the catalysts, Co2Ni-MOF@MX-1 achieved the best oxygen evolution performance with the lowest Tafel slope (51.7 mV dec-1) and the lowest overpotential (265 mV on carbon paper) at the current density of 10 mA cm-2. These results demonstrated that the synthesis of 2D composite materials by electrostatically directed assembly could be a feasible and promising method for the preparation of 2D heterostructure catalysts.

Recent Advances of Pore Structure in Disordered Carbons for Sodium Storage: A Mini Review.

Disordered carbons as the most promising anode materials for sodium ion batteries (SIBs) have attracted much attention, due to the widely-distributed sources and potentially high output voltage when applied in full cells owing to the almost lowest voltage plateau. The complex microstructure makes the sodium storage mechanism of disordered carbons controversial. Recently, many studies show that the plateau region of disordered carbons are closely related to the embedment of sodium ion/semimetal in nanopores. In this regard, the classification, characterization and construction of nanopores are exhaustively discussed in this review. In addition, perspectives about the controllable construction of nanopores are presented in the last section, aiming to catch out more valuable studies include not only the construction of closed pores to enhance capacity but also the design of carbon materials to understand Na storage mechanism.

Enabling fast-charging selenium-based aqueous batteries via conversion reaction with copper ions.

Selenium (Se) is an appealing alternative cathode material for secondary battery systems that recently attracted research interests in the electrochemical energy storage field due to its high theoretical specific capacity and good electronic conductivity. However, despite the relevant capacity contents reported in the literature, Se-based cathodes generally show poor rate capability behavior. To circumvent this issue, we propose a series of selenium@carbon (Se@C) composite positive electrode active materials capable of delivering a four-electron redox reaction when placed in contact with an aqueous copper-ion electrolyte solution (i.e., 0.5 M CuSO4) and copper or zinc foils as negative electrodes. The lab-scale Zn | |Se@C cell delivers a discharge voltage of about 1.2 V at 0.5 A g-1 and an initial discharge capacity of 1263 mAh gSe-1. Interestingly, when a specific charging current of 6 A g-1 is applied, the Zn | |Se@C cell delivers a stable discharge capacity of around 900 mAh gSe-1 independently from the discharge rate. Via physicochemical characterizations and first-principle calculations, we demonstrate that battery performance is strongly associated with the reversible structural changes occurring at the Se-based cathode.

Why does the capacity of vanadium selenide based aqueous zinc ion batteries continue to increase during long cycles?

At present, rechargeable aqueous zinc ion batteries (RZIBs) have become a rising star and highly sought after in the field of new energy. While vanadium-based RZIBs often exhibit an anomaly of increased long-cycle capacity, which has not been explored in depth. Nevertheless, it is critical to understand this phenomenon to develop high-performance RZIBs. Therefore, this study investigated the growth mechanism of VSe2-based RZIBs using VSe2/MXene as the cathode material via in-situ and ex-situ characterization techniques and electrochemical measurements. Experimental results indicated that with the interaction/extraction of Zn2+/H+ in the host material during cycling, an obvious oxidation reaction occurs at high voltage, and the formed vanadium oxide further reacts with Zn2+ from the electrolyte. As a result, Zn0.25V2O5·H2O is continuously produced and accumulated, contributing to the increasing capacity of the prepared RZIBs.

Reunderstanding the Reaction Mechanism of Aqueous Zn-Mn Batteries with Sulfate Electrolytes: Role of the Zinc Sulfate Hydroxide.

Rechargeable aqueous Zn-Mn batteries have garnered extensive attention for next-generation high-safety energy storage. However, the charge-storage chemistry of Zn-Mn batteries remains controversial. Prevailing mechanisms include conversion reaction and cation (de)intercalation in mild acid or neutral electrolytes, and a MnO2 /Mn2+ dissolution-deposition reaction in strong acidic electrolytes. Herein, a Zn4 SO4 ·(OH)6 ·xH2 O (ZSH)-assisted deposition-dissolution model is proposed to elucidate the reaction mechanism and capacity origin in Zn-Mn batteries based on mild acidic sulfate electrolytes. In this new model, the reversible capacity originates from a reversible conversion reaction between ZSH and Znx MnO(OH)2 nanosheets in which the MnO2 initiates the formation of ZSH but contributes negligibly to the apparent capacity. The role of ZSH in this new model is confirmed by a series of operando characterizations and by constructing Zn batteries using other cathode materials (including ZSH, ZnO, MgO, and CaO). This research may refresh the understanding of the most promising Zn-Mn batteries and guide the design of high-capacity aqueous Zn batteries.

Towards high performance room temperature sodium-sulfur batteries: Strategies to avoid shuttle effect.

Room temperature sodium-sulfur battery has high theoretical specific energy and low cost, so it has good application prospect. However, due to the disadvantageous reaction between soluble intermediate polysulfides and sodium anode, the capacity drops sharply, which greatly limits its practical application. In recent years, various strategies have been formulated to address the problem of polysulfides dissolution. This perspective article provides an overview of the research progress on research progress of novel cathode materials, multifunctional host, new electrolyte systems and modified separator/interlayer/anode. The challenge and prospect of the advanced strategies to suppress the polysulfides shuttle for long-life and high-efficiency room temperature sodium-sulfur batteries are proposed.

DTI Atlases Evaluations.

The cerebral atlas of diffusion tensor magnetic resonance image (DT-MRI, shorted as DTI) is one of the key issues in neuroimaging research. It is crucial for comparisons of neuronal structural integrity and connectivity across populations. Usually, the atlas is constructed by iteratively averaging the registered individual image. In tradition, the fuzzy group average image is easily generated in the initial stage, which is harmful to providing clear guidance for subsequent registration, to the performance of the final atlas. To solve this problem, an improved unbiased DTI atlas construction algorithm based on adaptive weights is proposed in this paper. The adaptive weighted strategy based on diffeomorphic deformable tensor registration is introduced. At the same time, the distance measure for tensors is used as a constraint condition, which ensures the unbiasedness of the atlas. Then, using 77 DTIs from the dataset in http://www.brain-development.org , three study-specific atlases, i.e. the constructed atlases of the proposed algorithm and two open-sourced algorithms (DTIAtlasBuilder and DTI-TK), are compared with two standardized atlases (IIT v. 4.1 and NTU-DSI-122-DTI). The performances of the atlases were evaluated in spatial normalization way with six region-based criteria (including Euclidean distances between diffusion tensors, Euclidean distances of the deviatoric tensors, standard deviation, overlaps of eigenvalue-eigenvector, cross-correlations and three sets angles of eigenvalue-eigenvector pairs between diffusion tensors) and three fiber-based criteria (including distances between fiber bundles, angles between fiber bundles and fiber property profile-based criteria). The experimental results showed that the overall performances of the study-specific atlases are better than those of the standardized atlases for specific datasets, and the comprehensive performance of the improved algorithm proposed in this paper is the best.

Hollow carbon spheres loaded with NiSe2 nanoplates as multifunctional SeS2 hosts for Li-SeS2 batteries.

Selenium sulfide as a new alternative cathode material can effectively address the inferior electronic conductivity of sulfur, which is the main cause for poor electrochemical reactivity of conventional lithium-sulfur batteries (Li-S batteries). Therefore, in this work, hollow carbon spheres loaded with NiSe2 nanoplates were prepared as SeS2 hosts for Li-SeS2 batteries. The unique micro-mesoporous hollow carbon spheres not only provide channels for the diffusion of SeS2, but also afford spaces for alleviating the volume expansion of the active substance. Besides, the external polar NiSe2 nanoplates increase active sites for capturing polysulfides or polyselenides during the charge/discharge process. Meanwhile, the excellent electronic conductivity of NiSe2 can accelerate the catalytic reaction on the surface, thus reducing the loss of soluble intermediate products and finally suppressing the "shuttle effect". These extraordinary features of the as-proposed cathode offer many superiorities in electrochemical performances in terms of a high initial discharge capacity of 1139 mA h g-1 at a current rate of 0.1C and an excellent cycling life of up to 1000 cycles at 1C.

Critical Role of Phosphorus in Hollow Structures Cobalt-Based Phosphides as Bifunctional Catalysts for Water Splitting.

Cobalt phosphides electrocatalysts have great potential for water splitting, but the unclear active sides hinder the further development of cobalt phosphides. Wherein, three different cobalt phosphides with the same hollow structure morphology (CoP-HS, CoP2 -HS, CoP3 -HS) based on the same sacrificial template of ZIF-67 are prepared. Surprisingly, these cobalt phosphides exhibit similar OER performances but quite different HER performances. The identical OER performance of these CoPx -HS in alkaline solution is attributed to the similar surface reconstruction to CoOOH. CoP-HS exhibits the best catalytic activity for HER among these CoPx -HS in both acidic and alkaline media, originating from the adjusted electronic density of phosphorus to affect absorption-desorption process on H. Moreover, the calculated ΔGH* based on P-sites of CoP-HS follows a quite similar trend with the normalized overpotential and Tafel slope, indicating the important role of P-sites for the HER process. Moreover, CoP-HS displays good performance (cell voltage of 1.67 V at a current density of 50 mA cm-2 ) and high stability in 1 M KOH. For the first time, this work detailly presents the critical role of phosphorus in cobalt-based phosphides for water splitting, which provides the guidance for future investigations on transition metal phosphides from material design to mechanism understanding.

A small molecule organic compound applied as an advanced anode material for lithium-ion batteries.

We choose copper(II) ions to salinize maleic acid, then form a layered copper maleate hydrate and apply this as an anode material for LIBs for the first time. The as-prepared material exhibits admirable electrochemical performance (404.6 mA h g-1 at 0.2 A g-1). A new hypothesis is developed for a better understanding of the unusual in situ XRD results and reaction mechanism.