Micro-mesoporous cobalt phosphosulfide (Co3S4/CoP/NC) nanowires for ultrahigh rate capacity and ultrastable sodium ion battery.

The construction of heterostructure materials has been demonstrated as the promising approach to design high-performance anode materials for sodium ion batteries (SIBs). Herein, micro-mesoporous cobalt phosphosulfide nanowires (Co3S4/CoP/NC) with Co3S4/CoP hetero-nanocrystals encapsulating into N-doped carbon frameworks were successfully synthesized via hydrothermal reaction and subsequent phosphosulfidation process. The obtained micro-mesoporous nanowires greatly improve the charge transport kinetics from the facilitation of the charge transport into the inner part of nanowire. When evaluated as SIBs anode material, the Co3S4/CoP/NC presents outstanding electrochemical performance and battery properties owing to the synergistic effect between Co3S4 and CoP nanocrystals and the conductive carbon frameworks. The electrode material delivers outstanding reversible rate capacity (722.33 mAh/g at 0.1 A/g) and excellent cycle stability with 522.22 mAh/g after 570 cycles at 5.0 A/g. Besides, the Ex-situ characterizations including XRD, XPS, and EIS further revealed and demonstrated the outstanding sodium ion storage mechanism of Co3S4/CoP/NC electrode. These findings pave a promising way for the development of novel metal phosphosulfide anodes with unexpected performance for SIBs and other alkali ion batteries.

Organic polymer coating induced multiple heteroatom-doped carbon framework confined Co1-xS@NPSC core-shell hexapod for advanced sodium/potassium ion batteries.

Synthesis of advanced structure and multiple heteroatom-doped carbon based heterostructure materials are the key to the preparation of high-performance energy storage electrode materials. Herein, the hexapod-shaped Co1-xS@NPSC has been triumphantly prepared using hexapod ZIF-67 as the sacrificial template to prepare Co1-xS inner core and N, P, and S tri-doped carbon (NPSC) as the shell through the carbonization of the organic polymer precursor. When applied as anode for Na+ batteries (SIBs) and K+ batteries (PIBs), Co1-xS@NPSC presents the high reversible specific capability of 747.4 mAh/g at 1.0 A/g after 235 cycles and 387.8 mAh/g at 5.0 A/g after 760 cycles for SIBs, as well as 326.7 mAh/g at 1.0 A/g after 180 cycles for PIBs. The excellent storage capacity and rate capability of Co1-xS@NPSC is ascribed to hexapod structure of ZIF-67 unlike the common dodecahedron, which is constructed with interior porous and exterior framework repository, donating supplemental active sites, and doping of multiple heteroatoms forming organic polymer coating inhibiting the volume expansion and restrains the agglomeration of Co1-xS nanoparticles. This approach has paved a bright avenue to exploit promising anode materials with novel structure and hetero-atom doping for high-performance energy storage devices.

Cobalt-vanadium sulfide yolk-shell nanocages from surface etching and ion-exchange of ZIF-67 for ultra-high rate-capability sodium ion battery.

Development of high-performance metal sulfides anode materials is a great challenge for sodium-ion batteries (SIBs). In this work, a cobalt-based imidazolate framework (ZIF-67) were firstly synthesized and applied as precursor. After the successive surface etching, ion exchange and sulfidation processes, the final cobalt-vanadium sulfide yolk-shell nanocages were obtained (CoS2/VS4@NC) with VS4 shell and CoS2 yolk encapsulated into nitrogen doped carbon frameworks. This yolk-shell nanocage structure effectively increases the specific surface area and provides enough space for inhibiting the volume change during charge/discharge processes. Besides, the nitrogen doped carbon skeleton greatly improves the ionic conductivity and facilitates ion transport. When used as the anode materials for SIBs, the yolk-shell nanocages of CoS2/VS4@NC electrode exhibits excellent rate capability and stable cycle performance. Notably, it displays a long-term cycling stability with excellent capacity of 417.28 mA h g-1 after 700 cycles at a high current density of 5 A/g. This developed approach here provides a new route for the design and synthesis of various yolk-shell nanocages nanomaterials from enormous MOFs with multitudinous compositions and morphologies and can be extended to the application into other secondary batteries and energy storage fields.

Synergistic enhancement of chemisorption and catalytic conversion in lithium-sulfur batteries via Co3Fe7/Co5.47N separator mediator.

Lithium-sulfur batteries (LSBs) show considerable potential in next-generation high performance batteries, but the heavy shuttle effect and sluggish redox kinetics of polysulfide hinder their further applications. In this paper, to address these shortcomings of LSBs, Co3Fe7/Co5.47N heterostructure were prepared and constructed from their Fe-Co Prussian blue analogue precursors under the condition of high temperature pyrolysis. The obtained Co3Fe7/Co5.47N display excellent immobilization-diffusion-conversion performance for polysulfides by synergistic effect in successfully hindering the shuttle effect of polysulfides. When the Co3Fe7/Co5.47N heterostructure were applied to modify the commercial polypropylene (PP) separator, the batteries displayed fantastic rate capacity and cycling stability. Specifically, the Co3Fe7/Co5.47N-PP batteries exhibit an extremely satisfactory initial specific capacity of 1430 m Ah/g at 0.5C, wonderful rate capacity of around 780 m Ah/g at 3C and superior per cycle decaying rate of 0.08 % for 500 cycles at 0.5C. When the current density reaches to 2C, the batteries still exhibit 501 m Ah/g after 900 cycles with 0.015 % per cycle decay rate. Besides, even in the high loading of sulfur (3.0 mg cm-2) at 0.5C, the superior cycling stability (0.075 % per cycle decay rate after 200 cycles) and high specific capacity (741 mAh/g after 200 cycles) can still be performed. Thus, this work provides a facile method for high-powered and long-life Li-S batteries with eminent entrapping-conversion processes of polysulfides.

Topochemical and phase transformation induced Co9S8/NC nanosheets for high-performance sodium-ion batteries.

In this paper, a cobalt-based sulfide nanosheet structure (Co9S8/NC) was successfully synthesized by topochemical and phase transformation processes from a dodecahedral cobalt-based imidazole skeleton (ZIF-67) as a self-template. The 2D sheet structure facilitates full contact of electrode materials with the electrolyte and shortens the diffusion distance for electrons and ions. In addition, the nitrogen-doped carbon framework derived from ZIF-67 promotes electron transfer and provides a reliable skeleton to buffer volume expansion during discharging and charging. Finally, Co9S8/NC exhibits excellent rate capability and stable cycling performance for the anode of a sodium ion battery, delivering a specific capacity remaining at 530 mA h g-1 after 130 cycles at a current density of 1 A g-1.

Modified separators boost polysulfides adsorption-catalysis in lithium-sulfur batteries from Ni@Co hetero-nanocrystals into CNT-porous carbon dual frameworks.

In this manuscript, nickel/cobalt bimetallic nanocrystals confining into three-dimensional interpenetrating dual-carbon conductive structure (NiCo@C/CNTs) were successfully manufactured by annealing its core-shell structure (Ni-ZIF-67@ZIF-8) precursor under the high temperature. The results presented that the bimetallic nickel and cobalt nanocrystals with superior catalytic activity could quickly convert solid Li2S/Li2S2into soluble LiPSs and effectively decrease the energy barrier. While the hierarchical CNT-porous carbon dual frameworks can provide quick electron/ion transport because of their large specific surface area and the exposure of enough active sites. When used as the separator modifier for lithium sulfur batteries, the battery properties were significantly improved with high specific capacity, outstanding rate capability, and long-term cycle stability. Specifically, its initial specific capacity can achieve to 1038.51 mAh g-1 at 0.5C. At the high rate of 3C, it still delivers satisfactory discharge capacity of 555 mAhg-1 and the capacity decay rate is only 0.065% per cycle after 1000 cycles at 1C. Furthermore, even exposed to heavy sulfur loading (3.61 mg/cm2), they still maintain promising cycle stability. Therefore, such kinds of MOFs derivative with powerful chemical immobilization and catalytic conversion for polysulfides provides a novel guidance for the modification separator and the potential application in the field of high-performance Li-S batteries.

ZnSe@NPSC core-shell nanorods for super sodium ion storage induced from an organic polymer derived N, P, S tri-doped carbon framework.

In this work, core-shell structured ZnSe@NPSC nanorods were prepared with a N, P, S hetero-doped carbon shell. The design of the core-shell structure is conducive to facilitating the transport of electrons and buffering the volume expansion during charge/discharge processes, which is favourable for improving the sodium ion storage properties of ZnSe@NPSC. Therefore, it can deliver capacities of 376.67 mA h g-1 after 150 cycles at 0.5 A g-1 and 359.1 mA h g-1 after cycling for 350 cycles at 1.0 A g-1, respectively.

Interface ion-exchange strategy of MXene@FeIn2S4 hetero-structure for super sodium ion half/full batteries.

Herein, a well-designed hierarchical architecture of bimetallic transition sulfide FeIn2S4 nanoparticles anchoring on the Ti3C2 MXene flakes has been prepared by cation exchange and subsequent high-temperature sulfidation processes. The introduction of MXene substrate with excellent conductivity not only accelerates the migration rate of Na+ to achieve fast reaction dynamics but provides abundant deposition sites for the FeIn2S4 nanoparticles. In addition, this hierarchical structure of MXene@FeIn2S4 can effectively restrain the accumulation of MXene to guarantee the maximized exposure of redox active sites into the electrolyte, and simultaneously relieve the volume expansion in the repeated discharging/charging processes. The MXene@FeIn2S4 displays outstanding rate capability (448.2 mAh g-1 at 5 A g-1) and stable long cycling performance (428.1 mAh g-1 at 2 A g-1 after 200 cycles). Moreover, the Nay-In6S7 phase detected by ex-situ XRD and XPS characterization may be regarded as a "buffer" to maintain the stability of the Fe-based components and enhance the reversibility of the electrochemical reaction. This work confirms the practicability of constructing the hierarchical structure bimetallic sulfides with the promising electrochemical performance.

Synergistic catalytic conversion and chemisorption of polysulfides from Fe/Fe3C/FeN0.0324 nanocubes modified separator for advanced Li-S batteries.

Lithium sulfur batteries (LSBs) have been considered as one of the most promising options for next generation high-performance batteries. However, the heavy shuttle effect and inferior redox conversion during the charge/discharge processes of the batteries have greatly hindered their further applications. In this study, to address these disadvantages of LSBs, Fe/Fe3C/FeN0.0324 heterostructured nanocubes were designed and prepared through high temperature carbonization process using Prussian blue precursor. Then the Fe/Fe3C/FeN0.0324 nanocubes were used to modify the commercial polypropylene (PP) separator, which can greatly catalyze the redox transformation of polysulfides and provide sufficient active sites for chemisorption. As result, the modified separator endowed LSBs with excellent rate capacity and cycle stability, delivering a high-capacity of 1025 mAh/g at 0.5 C with nearly 100% coulombic efficiency. It also displayed a superb cycling performance with a per-cycle capacity attenuation rate of 0.09% after 300 cycles. When the current density increased to 1 C with the S loading of 1.73 mg cm-2, Fe/Fe3C/FeN0.0324-PP separator presented a satisfactory capacity decay rate of 0.05% per cycle after 1000 cycles. Besides, it also presented outstanding electrochemical performance even at high sulfur loading of 4.5 mg cm-2. This work has provided a new avenue for the design of nanomaterials with synergistic effect of catalytic conversion and chemisorption of polysulfides for the promotion of high-performance Li-S batteries.

Hetero-structural and hetero-interfacial engineering of MXene@Bi2S3/Mo7S8 hybrid for advanced sodium/potassium-ion batteries.

Herein, heterogeneous bimetallic sulfides Bi2S3/Mo7S8 nanoparticles anchored on MXene (Ti3C2Tx) nanosheets (MXene@Bi2S3/Mo7S8) were prepared through a solvothermal process and subsequent chemical vapor deposition process. Benefiting from the heterogeneous structure between Bi2S3 and Mo7S8 and the high conductivity of the Ti3C2Tx nanosheets, the Na+ diffusion barrier and charge transfer resistance of this electrode are effectively decreased. Simultaneously, the hierarchical architectures of Bi2S3/Mo7S8 and Ti3C2Tx not only effectively inhibit the re-stacking of MXene and the agglomeration of bimetallic sulfides nanoparticles, but also dramatically relieve the volume expansion during the periodic charge/discharge processes. As a result, the MXene@Bi2S3/Mo7S8 heterostructure demonstrated remarkable rate capability (474.9 mAh/g at 5.0 A/g) and outstanding cycling stability (427.3 mAh/g after 1400 cycles at 1.0 A/g) for sodium ion battery. The Na+ storage mechanism and the multiple-step phase transition in the heterostructures are further clarified by the ex-situ XRD and XPS characterizations. This study paves a new way to design and exploit conversion/alloying type anodes of sodium ion batteries with hierarchical heterogeneous architecture and high-performance electrochemical properties.

Temperature and pressure sensitive ionic conductive triple-network hydrogel for high-durability dual signal sensors.

In this work, the fabrication of strengthened triple network hydrogels was successfully achieved based on in-situ polymerization of polyacrylamide by combining both chemical and physical cross-linking methods. The ion conductive phase of lithium chloride (LiCl) and solvent in the hydrogel were regulated through soaking solution. The pressure and temperature sensing behavior and durability of the hydrogel were investigated. The hydrogel containing 1 mol/L LiCl and 30 %v/v glycerol displayed a pressure sensitivity of 4.16 kPa-1 and a temperature sensitivity of 2.04 %/oC ranging from 20 to 50 °C. The durability results reveal that the hydrogel could maintain water retention rate of 69 % after 20 days of ageing. The presence of LiCl disrupted the interactions among water molecules and made it possible for the hydrogel to respond to changes in environment humidity. The dual signal testing revealed that the delay of temperature response over time (about 100 s) is much different from the rapidity of pressure response (in 0.5 s). This leads to the obvious separation of the temperature-pressure dual signal output. The assembled hydrogel sensor was further applied to monitor human motion and skin temperature. The signals can be distinguished by different resistance variation values and curve shapes in the typical temperature-pressure dual signal performance of human breathing. This demonstrates that this ion conductive hydrogel has the potential for application in flexible sensors and human-machine interfaces.

Synergistically enhanced sodium ion storage from encapsulating highly dispersed cobalt nanodots into N, P, S tri-doped hexapod carbon framework.

Development of multitudinous heteroatoms co-doped carbon nanomaterials with pleasurable electrochemical behavior for sodium ion batteries is still an enormous challenge. Herein, high dispersion cobalt nanodots encapsulating into N, P, S tri-doped hexapod carbon (H-Co@NPSC) have been victoriously synthesized via H-ZIF67@polymer template strategy with using poly (hexachlorocyclophos-phazene and 4,4'-sulfonyldiphenol) as both carbon source and N, P, S multiple heteroatom doping sources. The uniform distribution of cobalt nanodots and the Co-N bonds are conducive to form a high conductive network, which synergistically increase a lot adsorption sites and lessens the diffusion energy barrier, thereby improving the fast Na+ ions diffusion kinetics. Consequently, H-Co@NPSC delivers the reversible capacity of 311.1 mAh g-1 at 1 A g-1 after 450 cycles with 70% capacity storage rate, while obtains the capacity of 237.1 mAh g- 1 after 200 cycles at the elevated current densities of 5 A g-1 as an excellent anode material for SIBs. These interesting results pave a generous avenue for the exploitation of promising carbon anode materials for Na+ storage.

1D hybrid metal coordination polymer-derived hierarchical Co1-xS/MnS/NC nanowires for advanced sodium-ion batteries.

Hierarchical Co1-xS/MnS/NC nanowires have been successfully prepared by a simple hydrothermal reaction and the subsequent annealing process of its one-dimensional (1D) coordination polymer precursors. The Co1-x/MnS/NC heterostructure nanowires can not only buffer the volume expansion during the discharging and charging process but also conspicuously enhance electronic conductivity, which is favourable for improving the rate performance and cycling stability, which can maintain 612.9 mA h g-1 after 100 cycles at 0.5 A g-1 and 544.6 mA h g-1 after 200 cycles at 1.0 A g-1 for SIBs.

Selenide-doped bismuth sulfides (Bi2S3-xSex) and their hierarchical heterostructure with ReS2for sodium/potassium-ion batteries.

In this work, selenide-doped bismuth sulfides (Bi2S3-xSex) was successfully prepared through Se doping Bi2S3 Se to improve the electronic conductivity and increase the interlayer spacing. Then the anisotropic ReS2 nanosheet arrays were grown on the surface of Bi2S3-xSex to form a hierarchical heterostructure (Bi2S3-xSex@ReS2). The doping and construction of heterostructure processes can greatly improve the electrochemical conductivity of electrode materials and relieve the volume expansion during the continuous charge/discharge processes. While applied as SIBs anode, the specific capacity of 330 mAh g-1 was maintained after 450 cycles at the current density of 1.0 A g-1. It can also keep 200 mAh g-1 specific capacity after 900 cycles at 1.0 A g-1 for the anode of PIBs. This heterogeneous engineering and doping dual strategies could provide a good idea for the synthesis of new bimetallic sulfides with outstanding battery performance for SIBs and PIBs.

Heterostructure and doping dual strategies engineering of MoS1.5Se0.5@VS2 nanosheets aggregated nano-roses for super sodium-ion batteries.

Herein, selenium (Se)-doped MoS1.5Se0.5@VS2 nanosheets aggregated nano-roses were successfully prepared from a simple hydrothermal process and the subsequent selenium doping process. The hetero-interfaces between MoS1.5Se0.5 and VS2 phase can effectively promote the charge transfer. Meanwhile, the different redox potentials of MoS1.5Se0.5 and VS2 alleviate volume expansion during the repeated sodiation/desodiation processes, which improves the electrochemical reaction kinetics and structural stability of electrode material. Besides, Se doping can induce charge reconstruction and improve the conductivity of electrode materials, resulting in improved diffusion reaction kinetics by expanding interlayer spacing and exposing more active sites. When used as anode material for sodium ion batteries (SIBs), the MoS1.5Se0.5@VS2 heterostructure exhibits excellent rate capability and long-term cycling stability with the capacity of 533.9 mAh g-1 at 0.5 A g-1 and a reversible capacity of 424.5 mAh g-1 after 1000 cycles at 5 A g-1, demonstrating potential application as anode material for SIBs.

Progressive activation of porous vanadium nitride microspheres with intercalation-conversion reactions toward high performance over a wide temperature range for zinc-ion batteries.

Rechargeable aqueous zinc-ion batteries have great promise for becoming next-generation storage systems, although the irreversible intercalation of Zn2+ and sluggish reaction kinetics impede their wide application. Therefore, it is urgent to develop highly reversible zinc-ion batteries. In this work, we modulate the morphology of vanadium nitride (VN) with different molar amounts of cetyltrimethylammonium bromide (CTAB). The optimal electrode has porous architecture and excellent electrical conductivity, which can alleviate volume expansion/contraction and allow for fast ion transmission during the Zn2+ storage process. Furthermore, the CTAB-modified VN cathode undergoes a phase transition that provides a better framework for vanadium oxide (VOx). With the same mass of VN and VOx, VN provides more active material after phase conversion due to the molar mass of the N atom being less than that of the O atom, thus increasing the capacity. As expected, the cathode displays an excellent electrochemical performance of 272 mAh g-1 at 5 A g-1, high cycling stability up to 7000 cycles, and excellent performance over a wide temperature range. This discovery creates new possibilities for the development of high-performance multivalent ion aqueous cathodes with rapid reaction mechanisms.

MOF derived cobalt-nickel bimetallic phosphide (CoNiP) modified separator to enhance the polysulfide adsorption-catalysis for superior lithium-sulfur batteries.

Lithium-sulfur batteries (LSBs) have aroused great research interest due to their high theoretical capacity and high energy density. To further develop lithium-sulfur batteries, it has become more and more important to put more efforts in promoting the adsorption and rapid catalytic conversion of lithium polysulfides (LiPSs). Herein, Ni/Co bimetallic phosphides were encapsulated into nitrogen-doped dual carbon conductive network (NiCoP@NC) by annealing and phosphorizing Ni-ZIF-67 precursor at high temperature. Due to their numerous co-adsorption/catalytic sites and high conductivity of carbon skeleton, the encapsulated Ni/Co phosphides particles could significantly enhance the anchoring and catalytic conversion of LiPSs and provide ultrafast channels for Li+ transport. When used as a modified separator for LSBs, the cells displayed superior performance with an initial capacity of 1083.4 m Ah g-1 at 0.5 C and outstanding cycle stability with a capacity decay rate of only 0.09% per cycle for 300 cycles. Besides, even at high sulfur loading (3.2 mg cm-2), they still present satisfactory performance. Therefore, this study presents a novel strategy on how to use MOF derived bimetallic phosphides with chemical adsorption and catalytic conversion of polysulfides for high-power advanced lithium-sulfur batteries.

Defect engineering of molybdenum disulfide nanosheets boosting super Zn2+ storage from polyaniline intercalation.

In this work, peony-like structured MoS2 with intercalation of polyaniline and crystal defects was prepared by a simple hydrothermal method. The defect-rich structure and broad interlayer distance can effectively provide vast ion transport paths to enhance the ion diffusion rate. PA-MoS2 can maintain 157.7 mA h g-1 at 0.1 A g-1 after 80 cycles and 77.8 mA h g-1 at 1 A g-1 after 750 cycles.

Multilayer structure covalent organic frameworks (COFs) linking by double functional groups for advanced K+ batteries.

Covalent organic frameworks (COFs) are regarded as the potential and promising anode materials for potassium ion batteries (PIBs) on account of their robust and porous crystalline structure. In this work, multilayer structural COF connected by double functional groups, including imine and amidogent through a simple solvothermalprocess, have been successfully synthesized. The multilayer structure of COF can provide fast charge transfer and combine the merits of imine (the restraint of irreversible dissolution) and amidogent (the supply of more active sites). It presents superior potassium storage performance, including the high reversible capacity of 229.5 mAh g-1 at 0.2 A g-1 and outstanding cycling stability of 106.1 mAh g-1 at the high current density of 5.0 A g-1 after 2000 cycles, which is superior to the individual COF. The structural advantages of the covalent organic framework linking by double functional groups (d-COF) can develop a new road for that COF anode material for PIBs in further research.

Cobalt-nickel bimetallic sulfide (NiS2/CoS2) based dual-carbon framework for super sodium ion storage.

Design hybrid metal sulfides-based anode materials is one of the most effective approaches to improve the performance of sodium-ion batteries (SIBs). However, owing to the huge volume expansion, the capacity of sulfide-based anode will decay significantly after repeated charge/discharge processes. Herein, we reported the successful demonstration of anode material based on concaved NiS2@CoS2 nanocube (NCSC) via a chemical etching strategy, which was derived from etching and sulfidation of Ni-Co coordination polymers (NiCoCP) precursor. The obtained NCSC anode materials deliver a high specific sodium storage capacity of 848 mAh g-1 at 0.1 A g-1 and a stable cyclability of 572 mAh g-1 at 5 A g-1 after 830 cycles. This special etching strategy exploit a novel way for the design and preparation of high-performance anode materials for SIBs.