In recent years, metal phosphosulfides have attracted great attention as the promising anode materials in sodium/potassium batteries because of their incorporation of the advantages of metal phosphides and sulfides. However, they are also confronted with the problem of unstable battery performance due to the heavy volume expansion and sluggish ion reaction kinetics. Herein, yolk-shell cobalt phosphosulfide nanocrystals encapsulating into multi-heterogeneous atom (N, P, S)-doped carbon framework (Co9S8/CoP@NPSC) were constructed by employing dodecahedral ZIF-67 as precursor and a polymer as carbon sources through simultaneous sulfidation and phosphorization processes. The synergistic effect of Co9S8 and CoP component and the yolk-shell structure greatly improve the bettery performance and structural stability. In addition, the multiple hetero-atoms doped carbon frameworks enhance the conductivity of the electrode materials and increase the spacing of carbon layers to supply sufficient active sites and facilitate the Na+/K+ transport. The electrochemical results demonstrated that Co9S8/CoP@NPSC exhibited the pleasant reversible capacity (360.47 mAh/g at 1 A/g) after 300 cycles and an unpredictable cycling stability (103.22 mAh/g after 1000 cycles) in the SIBs application. The ex-situ XRD and XPS analyses were further applied to study the sodium ion storage mechanism and the multi-step phase transition reaction of the yolk-shell heterogeneous structure. This work provides new perspectives for the preparation of novel structure metal phosphosulfide and their applications in anode materials for sodium/potassium batteries and other secondary batteries.

Metal phosphosulfides have been recognized as advanced anode materials for sodium/potassium ion batteries due to their high theoretical capacities and the incorporation of the advantage of metal sulfides and phosphates. However, they also suffer from the shortcomings of frustrating cycling stability due to the large volume expansion and unsatisfactory electrical conductivity. Herein, hexapod cobalt phosphosulfide nanodots based nanorods encapsulating into N, P, and S hetero-atoms tri-doped carbon framework (CoP/CoS2@NPSC) have been triumphantly designed and synthesized. The six nanorods constructed hexapod framework and multi-atom doped carbon matrix not only provides more active sites, but also contribute to maintain the structure integrity from avoiding the agglomeration of internal CoP and CoS2 nanodots. The synergistic effect between CoP and CoS2 components, as well as the CoP/CoS2 and the NPSC carbon framework can improve the electrochemical conductivity. Besides, the kinetics analysis demonstrated that N/P/S tri-doping could greatly increase the interlayer distance and introduce enough active sites, which effectively facilitate the transport, adsorption, insertion and diffusion of Na+ and K+. CoP/CoS2@NPSC demonstrated excellent electrochemical properties and battery performances including excellent cycle stability with 404.63 mAh/g at 5.0 A/g around 700 cycles for SIBs and 115.33 mAh/g at 5.0 A/g around 800 cycles for PIBs. This presented strategy establishes a novel and adaptable method for the integration of doped carbon with metal phosphosulfide and guides a new research approach and direction for secondary batteries electrode materials.

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.

As the most promising anodes for Na+/K+ batteries (SIBs/PIBs), transitional metal sulfides present the advantages of high capacity, straightforwardly-controlled morphology and abundant redox reaction sites. However, maintaining the structural integrity of the electrode materials during cycling and improving the cycle life still face great challenges. Herein, CoS2@NPSC@MoS2 nano-spindle heterostructure with multiple heteroatoms co-doped carbon layers coupled with Janus metal sulfides (CoS2 and MoS2) were successfully fabricated via the successive organic coating, gas-phase phosphorization and the final hydrothermal reaction processes. Benefiting from the uniformly dispersed CoS2 nanocrystals in the interior of carbon layer and the MoS2 nanosheets arrays in the exterior, Na+/K+ diffusion distances are remarkedly shortened and the reaction kinetics are greatly improved, which also provide more active sites on the surface for exposure to the electrolyte. The presence of heterogeneous atomic N/P/S co-doped carbon layer greatly improves the electrochemical conductivity of the heterostructure and provide additional buffer space for volume changes, which is conducive to retaining the integrity of the electrode structure during the cycling processes. When used as the anode material for SIBs/PIBs, it reached the reversible specific capacity of 340.44 mAh g-1 at 5.0 A g-1 after 1000 cycles for SIBs and 37.53 mAh g-1 at 5.0 A g-1 after 800 cycles for PIBs. This work demonstrates a reliable and simple strategy for the rational design of Janus metal sulfides heterostructures for high performance Na+/K+ storage application.

In this paper, heterogeneous cobalt phosphosulfide (Co4S3/Co2P) nanocrystals anchoring on few-layered MXene nanosheets (MXene@Co4S3/Co2P) were prepared by in situ growth and the subsequent high-temperature phosphorization/sulfidation processes. Thanks to the synergistic effect and the abundant phase interfaces of Co4S3, Co2P, and MXene, the electron transfer and Na+ diffusion processes were greatly accelerated. Meanwhile, the high electrical conductivity of MXene nanosheets and the heterogeneous structure of Co4S3/Co2P effectively avoided the MXene restacking and the agglomeration of phosphosulfide particles, thus mitigating volumetric expansion during charging and discharging. The results show that the MXene@Co4S3/Co2P heterostructure presents good rate capability (251.08 mAh g-1 at 1 A g-1) and excellent cycling stability (198.69 mAh g-1 after 407 cycles at 5 A g-1). Finally, the storage mechanism of Na+ in the heterostructure and the multistep phase transition reaction were determined by ex situ X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and X-ray photoelectron spectroscopy (XPS) analyses. This study provides a new perspective on the formation of metal phosphosulfide and MXene hybrids with multiple heterointerfaces as well as demonstrates MXene@Co4S3/Co2P composites as the promising anode material in sodium-ion batteries.

Na+ batteries (SIBs) have been emerging as the most promising candidate for the next generation of secondary batteries. However, the development of high-performance and cost-effective anode materials is urgently needed for the large-scale applications of SIBs. In this study, carbon dots confined bimetallic sulfide (NiCo2S4) architecture (NiCo2S4@CDs) was proposed and synthesized from assembling nanosheets into cross-stacked superstructure and the subsequent confinement of carbon dots. This novel decussated structure assembly from nanosheets is greatly beneficial to the structure stability of electrode material during the successive charge/discharge processes. Besides, the CDs based carbon conductive network can enhance the electrical conductivity for facilitating the easy transport of electron/Na+. Benefitting from these advantages, NiCo2S4@CDs exhibits high-rate performance and an ultralong cycling life in SIBs. Specifically, the specific capacity of NiCo2S4@CDs can reach the discharge specific capacity as high as 568.9 mAh/g at 0.5 A/g, which can also maintain 302.7 mAh/g after 750 cycles at 5.0 A/g. Additionally, ex-situ characterization techniques such as ex-situ XRD and ex-situ XPS were employed to further explore the sodium storage mechanism of the NiCo2S4@CDs anode.

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.

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.

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.

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.