Significantly enhanced ion‐migration and sodium‐storage capability derived by strongly coupled dual interfacial engineering in heterogeneous bimetallic sulfides with densified carbon matrix

The development of highly efficient sodium‐ion batteries depends critically on the successful exploitation of advanced anode hosts that is capable of overcoming sluggish reaction kinetics while also withstanding severe structural deformation triggered by the large radius of Na+‐insertion. Herein, a hierarchically hybrid material with hetero‐Co3S4/NiS hollow nanosphere packaged into a densified N‐doped carbon matrix (Co3S4/NiS@N‐C) was designed and fabricated utilizing CoNi‐glycerate as the self‐sacrifice template, making the utmost of the synergistic effect of hetero‐Co3S4/NiS with strong electric field and rich reaction active‐sites together with the densified outer‐carbon scaffolds with remarkable electronic conductivity and robust mechanical toughness. As anticipated, as‐fabricated Co3S4/NiS@N‐C anode affords remarkable specific capacity, prolonged cycle lifespan up to 2 400 cycles with an only 0.05% fading each cycle at 20.0 A g−1, and excellent rate feature (354.9 mAh g−1 at 30.0 A g−1), one of the best performances for most existing Co3S4/NiS‐based anodes. Ex situ structural characterizations in tandem with theoretical analysis demonstrate the reversible insertion‐conversion mechanism of initially proceeding with Na+ de‐/intercalation and superior heterogeneous interfacial reaction behavior with strong Na+‐adsorption ability. Further, sodium‐ion full cell and hybrid capacitor based on Co3S4/NiS@N‐C anode exhibit impressive electrochemical characteristics on cycling performance and rate capability, showcasing its outstanding feasibility toward practical use.


INTRODUCTION
][6][7][8][9][10] The widespread commercial use of SIBs is however faced with the significant challenges, involving poor electrochemical activity, relatively great ion-diffusion barrier, and gravimetric energy density of anode materials, mainly thanks to larger ion-radius and heavier ionic-weigh of Na + in comparison to Li + . 11,12Under these circumstances, frontier efforts toward exploiting SIBs anodes have primarily highlighted on the efficient use of double-type reaction-based anode matter (e.g., insertion-conversion or conversionalloy), enabling SIBs to match existing LIBs in energy densities. 13,146][17] Meanwhile, the final conversion product Na 2 S formed by TMCs during the charge-discharge reaction is more conductive than discharge product Na 2 O of oxide counterparts, kinetically facilitating better ion-diffusion and electrochemical activity. 18,19Not only that TMCs have a higher specific capacity and better safety in comparison to anode matter based on single intercalation-type Na + -storage materials (such as carbon anode) since they prevent the formation of sodium dendrite in the low voltage area. 20Of the reported TMCs represented by Ni/Co-based anodes, famous for the intercalation-conversion mechanism, have distinguished themselves as desired contenders for SIBs by virtue of their outstanding theoretical capacity, strong redox activity, easy fabrication, and cost-effectiveness. 21,22And a step further is the Ni/Co-based TMCs with diverse structural forms and more elemental valence states that can endow more abundant Na + -storage sites.Unfortunately, three main obstacles associated with inferior kinetics brought by inherent poor conductivity, restricted cyclability on account of the significant volume fluctuation and new phases formation, together with the polysulfides dissolution in electrolyte during the repeated Na + -insertion still heavily restricted their practical application. 23,24The ion conductivity and swift ion-transport velocity are generally very important factors that determine a material's ability to store energy. 25,26Hence, it is of great significance and urgency to synthesize and build a unique Ni/Co-based TMCs anode with better electronic/ionic transfer rate, aiming to provide exceptional durability and sufficient rate capability.
As reported, the decoration of the carbon matrix with active electrode materials is feasible for substantially increasing reaction kinetics, alleviating the unavoidable pulverization brought by the drastic structural distortion, and stabilizing solid-electrolyte interphase (SEI). 27,28ore specifically, heteroatom-doped carbon matrix can increase active sites for Na + -storage, change the electron feature of the carbon matrix, and increase the interlayer distance, making it easier for electron to conduct in active materials. 29Although carbon-based TMCs hybrid structures perform better electrochemically, while the conventional carbon modification above was concentrated on the external interface regulation or conductive substrate to stabilize the electrode structure and facilitate interparticle electronic/ionic diffusion on the electrode surface, which cannot effectively expedite rapid iontransport between the crystal structure, thereby restricting further enhancement of Na + -storage ability for carbonbased TMCs hybrids. 30,31Recently reported demonstrates that constructing multicomponent sulfides utilizing two kinds of diverse electronic band-gap components are regarded as one of the most efficient intrinsic crystalinterface models to promote the internal charge-transfer and ion-transport. 32,33Indeed, the existence of heterointerface helps to stabilize the structural stability and avoid the agglomeration of metal nanoparticles produced by the conversion reaction, which improved reversibility and species absorptivity.Meanwhile, a localized built-in electric field is spontaneously generated on the interface by such a heterogeneous boundary, which significantly enhance electronic conductivity and charge carrier mobility, resulting in a rapid ion shuttle rate and strong energy storage capabilities. 34,35What's more impressive is that the heterogeneous structure not only contains rich phase interfaces that can contribute to excess capacity by creating specific capacitance effects and additional ion storage sites, 36 but also the out-of-step redox voltages and electrochemical reactions of multicomponent can afford significant electrochemical activity and decrease volumetric strain as a result of the complementary and synergistic interaction between the reaction products. 37,38It is therefore very desirable, but still faces tremendous challenge, for exploiting multicomponent composites with heterojunction and hierarchical carbon decoration to resolve major bottlenecks upon the cycling through the collaborative mechanism between the components.
Enlighted from above analysis, we put forward a straightforward method for designing a hierarchically hybrid material with hetero-Co 3 S 4 /NiS hollow nanosphere encapsulated into an ultrathin N-doped carbon matrix (Co 3 S 4 /NiS@N-C), which establishes a compacted spatial geometry configuration via a combination strategy of vulcanization, in situ dopamine polymerization, and carbonization involving CoNi-glycerate as the template.This specially hierarchical hybrid structure has the significant ability that can induce swift charge-transfer and ion-migration, afford abundant Na + -transport channels, as well as supply an adequate number of active sites and electrode/electrolyte contact interface.Additionally, the volumetric strain of the electrode can also be simultaneously cushioned by the strong coupling interaction of the multiphase constituent particularly as cycled at high rate.Results from the theoretical analysis and ex situ characterization further expound the electrochemical reaction mechanism and the interplay between carbon decoration and heterostructure.Consequently, asfabricated Co 3 S 4 /NiS@N-C anode manifests remarkable Na + -storage characteristics from the perspective of rate capability, reversible capacity, and cyclic lifespan.

RESULTS AND DISCUSSION
As manifested schematically in Figure 1A, a multi-step construction strategy was implemented to controllably fabricate the Co 3 S 4 /NiS@N-C composites.Specifically, the CoNi-glycerate solid nanospheres (CoNi-G, Figure 1B,C), Co-glycerate solid nanospheres (Co-G, Figure S1), and Ni-glycerate solid nanospheres (Ni-G, Figure S2) were selected as the precursor and synthesized via a facial hydrothermal method, which all present the uniform geometric nanospherical structure and monodisperse characteristic with smooth surface as confirmed by the field-emission scanning electrode microscopy (FESEM).
Taking CoNi-G as an example, transmission electron microscopy (TEM) images in Figure 1D,E demonstrate its solid nature with a uniform diameter particle size of ∼500 nm.Subsequently, CoNi 2 S 4 products were produced via hydrothermally induced chemical etching/anion exchange between CoNi-G and thioacetamide solution.As seen, the CoNi 2 S 4 sample well maintains the nanosphere shape of CoNi-G precursor (Figure S3a,b), presenting its superior structure stability.Meanwhile, the relatively rough surface and significant cavity region are visible in the TEM image of CoNi 2 S 4 sample (Figure S3c).Besides, each CoNi 2 S 4 nanosphere has an average particle size of ∼600 nm in diameter and a cavity wall of ∼20 nm in thickness.According to the high-resolution transmission electron microscopy (HRTEM) image (Figure S3d), three types of interplanar spacings, involving (4 0 0), (1 1 1), and (2 2 0) facets, exist in the CoNi 2 S 4 nanospheres, demonstrating the successful synthesis of cubic CoNi 2 S 4 , which can be further verified through X-ray diffraction (XRD) test (Figure S4).With the completion of in situ dopamine polymerization (Figure S5) and gas-phase carbonization procedure, an ultrathin and densified N-doped conductive carbon matrix was created by pyrolyzing dopamine (PDA), giving rise to the end-product Co 3 S 4 /NiS@N-C heterostructure.As revealed in Figure 1F,G, the Co 3 S 4 /NiS@N-C composites almost maintain the same spherical architecture characteristic as hollow CoNi 2 S 4 nanosphere without any structural agglomeration and damage, and meanwhile the average particle size of Co 3 S 4 /NiS@N-C is nearly equal to that of CoNi 2 S 4 @PDA.Further examination by TEM shows several regular hollow Co 3 S 4 /NiS sphere structure, which can be further wrapped through a uniform dense carbon layer of ∼20 nm (Figure 1H-J).As the control sample, the FESEM and TEM images of hollow Co 3 S 4 /NiS nanospheres in Figure S6 show that the surface of nanospheres is rougher and there are obvious structural damage due to the absence of the outer-carbon matrix.A distinct phase boundary can be seen by comparing two different types of interplanar spacings, according to the HRTEM picture (Figure 1K).Two sets of distinct lattice fringes, which are 0.267 and 0.550 nm, respectively, are readily good coincidence in the (1 0 1) plane of NiS and the (1 1 1) plane of Co 3 S 4 , indicating the co-presence of NiS and Co 3 S 4 .
The selected area electron diffraction (SAED) pattern also further signifies the presence of the polycrystalline nature for binary sulfides (Figure 1L), matching well with the (1 0 1) and ( 1 Through TEM observation, the Co 3 S 4 sample exhibits a significant yolk-shell structure configuration (Figure S7c).For bare NiS sample, although the geometric hollow spherical feature is monitored, while the spherical surface is composed of many nanoparticles (Figure S8).
The XRD test was used to determine the substance composition and phase purity of as-constructed samples.In Figure 2A, all the reflections appeared in bare Co 3 S 4 and NiS samples are in good accordance with the standard patterns of cubic Co 3 S 4 (JCPDS # 42-1448) and hexagonal NiS (JCPDS # 02-1280).Whereas for the heterogeneous two samples, the (2 2 0), (3 1 1), (4 0 0), (5 1 1), and (4 4 0) planes of cubic Co 3 S 4 are, respectively, responsible for the reflection signals at 26.7  , and 53.5 • , assignable to the (1 0 0), (1 0 1), (1 0 2), and (1 1 0) facets, originate from the NiS, symbolizing the successful construction of the bimetallic sulfides heterostructure.Two noticeable shifts in the Raman spectrum of Co 3 S 4 /NiS@N-C composites, depicted in Figure 2B, are visible at ≈1 386.6 cm −1 (disordered graphitic carbon) and 1 585.1 cm −1 (sp 2 hybridized graphitic carbon), which, depending on the carbon substance, is categorized as the D-band and the G-band, respectively. 39Meanwhile, estimating the unordered degree of carbonaceous substance involved computing the I D /I G proportion, thus, the computed value of I D /I G for the Co 3 S 4 /NiS@N-C composites is ∼0.99, suggesting that surface carbon atom structure is influenced by sufficiently high conductivity and more polar C-N/C-S species.Besides, the existence of NiS is a main reason for three relatively weak characteristic signals that emerged in a low wavenumber in the Raman spectrogram of Co 3 S 4 /NiS@N-C composites.In particular, the peaks at around 506.3 and 673.1 cm −1 might be connected to the Ni-S bond mode, 40,41 whereas the peak at 428.9 cm −1 is interpreted as the stretching mode of the S-S pair. 42,43The N 2 adsorption-desorption experiments of four samples and the matching pore size distribution are presented in Figure 2C,D, one can see that the representative IV adsorption/desorption isotherms with clear hysteresis loop that appear at the P/P 0 of 0.70-0.95suggest the mesoporous structure existed in these samples.On the basis of the measurement results, Brunauer-Emmett-Teller surface area of Co 3 S 4 /NiS@N-C, Co 3 S 4 /NiS, bare Co 3 S 4 , and NiS were determined to be about 29.4,8.86, 25.3, and 10.8 m 2 g −1 , with the majority of pore diameters at 18.4, 30.6, 19.4, and 26.9 nm, respectively.Such superior mesoporous structure and comparatively large surface area of Co 3 S 4 /NiS@N-C composites offer essential advantages for the complete penetration of the electrolyte and fast Na + -transport and charge transference rate, guaranteeing a greater contact area between the electrode and electrolyte, and thereby efficiently enhancing the electrochemical activity.The carbon content in Co 3 S 4 /NiS@N-C composites was verified using thermal gravimetric (TG) technique (Figure 2E).Obviously, surface water desorption is responsible for a small weight loss (2.68 wt%) of the sample below 200 • C. Following that, a significant drop in weight occurs in a range of 350 • C-550 • C, which could potentially be attributable to the combination of carbon with oxygen to form carbon dioxide.The main weight loss at 650 • C-800 • C is due to the formation of NiO and Co 3 O 4 during the oxidation reaction, 44,45 the calculated amount of the carbon matrix was estimated to be ∼34.9%.X-ray photoelectron spectroscopy (XPS) was proceeded to ascertain the bonding configuration and electronic coupling effect in more detail between Co 3 S 4 and NiS.As depicted in full survey spectra of Figure 2F, the reflection signals of all the elements in four samples can be found.Note that the as-prepared sample will inevitably be exposed to air, which result in the superficial oxidation of the metal sulfides to produce amorphous metal oxides.More importantly, XPS is a surface analysis technique, and the analysis depth of conventional tests is usually around 10 nm, thus inducing the presence of a significant O 1s peak in the survey XPS spectrum.Two peaks, Co 2+ 2p 3/2 at 781.8 eV and Co 2+ 2p 1/2 at 797.9 eV, are shown in Figure 2G for high-resolution Co 2p spectra, while the other peaks associated with Co 3+ 2p 3/2 and Co 3+ 2p 1/2 are linked to binding energies of 779.4 and 794.4 eV, respectively. 18Similarly, two valence states related to Ni 2+ and Ni 3+ in the high-resolution Ni 2p spectra are discernible (Figure 2H), where two doublets at 854.1 and 871.5 eV are, respectively, linked to Ni 2+ 2p 3/2 and Ni 2+ 2p 1/2 orbitals, while another group of distinctive peaks at 856.8 and 874.8 eV connected with Ni 3+ 2p 3/2 and Ni 3+ 2p 1/2 orbitals, respectively. 44,46Regarding the S 2p spectra (Figure 2I), four fitted peaks at 161.5, 162.4,163.8, and 168.3 eV are, respectively, attributable to the S 2p 3/2 and S 2p 1/2 orbitals of divalent sulfide ions, thiophene-S, and SO x species. 35,47Notably, a special peak signal centered at 164.8 eV position of Co 3 S 4 /NiS@N-C can be correspond to C-S/C = S bonds. 39,48The peaks at 284.8, 285.2, 286.4,and 288.3 eV, which are associated with the C-C, C = C, C-S/C-N, and C = O, respectively, [49][50][51] can be fitted to the high-resolution C 1s spectrum in Figure S9a.The successful doping of the carbon matrix by N and S atoms can generate plentiful active sites to accommodate more Na + , and distinctly accelerate the electronic transfer efficiency.As for N 1s spectrum (Figure S9b), three peaks are visible, representing pyridinic-N (398.5 eV), pyrrolic-N (400.2 eV), and quaternary-N (401.1 eV). 52clic voltammetry (CV) profiles for first three cycles of Co 3 S 4 /NiS@N-C composites in conjunction with the reference samples, that is, Co 3 S 4 /NiS (Figure S10a), Co 3 S 4 (Figure S10b), and NiS (Figure S10c) were tested at 0.5 mV s −1 to collect their redox mechanism during the Na +insertion.As for Co 3 S 4 /NiS@N-C electrode (Figure 3A), the insertion of Na + into the Co 3 S 4 crystal structure to stimulate the formation of Na x Co 3 S 4 is a dominant reason that causes the first-cycle peak to occur at 1.25 V in the first cathodic scan thanks to the conversion of Co 3 S 4 , 53,54 and then this peak shift to 1.40 V in the following cycles.Besides, the reduction of NiS to Ni 3 S 2 that is forming on the initial Na + -insertion stage is what induces a sharp peak emerged at 1.13 V. 55 While the successive conversion of Na x Co 3 S 4 and Ni 3 S 2 to Ni, Co, and Na 2 S accompanied with the formation of the SEI layer well affords persuasive explanation for the observed broad reduction peak spanning from 0.50 to 0.90 V. 18 In the first anodic scan, the corresponding oxidation peaks occurred at 1.76, 1.95, and 2.09 V are attributable to the desalting reaction to form Co 3 S 4 and NiS.The well-preserved CV curves in subsequent cycles indicate that the sodiation/desodiation reaction of Co 3 S 4 /NiS@N-C electrode exhibits strong reversibility following the initial activation cycle.Ex situ XPS analysis was applied to ascertain the elemental valence for the cycled electrodes during the oxidation and reduction.The high-resolution Co 2p spectra in Figure 3B reveal that when the electrode was discharged from 1.0 V to a fully stated 0.01 V, the Co 2+ 2p 1/2 peak clearly moves to a low binding energy, simultaneously the Co 2+ 2p peak areas gradually decreases, signifying the partial oxidation of Co (II) to Co (III).More significantly, a noticeable distinctive peak signal associated with Co 0 2p 3/2 appears, 56 indexing to the formation of metallic Co and Na 2 S from the conversion reaction of Co 3 S 4 and Na + .When the charge reaches its maximum, Co 2+ 2p recovers to its original state proving well reversibility.A similar changing trend is seen in the high-resolution Ni 2p spectra (Figure 3C).The distinctive Ni 0 2p 3/2 species peak at around 856.3 eV is identified after the battery was fully discharged to 0.01 V, followed by completely vanish as the voltage changed to 3.0 V. 57,58 A series of distinctive signal peaks that are connected to polythionate and thiosulfate were seen from the high-resolution S 2p spectra (Figure 3D), which are found in the bonding-energy region of 166 ∼172 eV. 16In addition, the emergence of polar S 2 2-and S 2 n-bond at 162-164.5 eV indicates the high chemical adsorption capabilities at the fully charged state of 3.0 V. 59 Further, a comprehensive understanding of voltage-dependent fundamental phase change and Na-storage mechanism of Co 3 S 4 /NiS@N-C upon the first sodiation/desodiation was obtained through the combination of a suite of ex situ characterizations, such as XRD, HRTEM, and SAED patterns.It is significant to bear in mind that, to increase the peak signal intensity of intermediate product, ex situ XRD signals of Co 3 S 4 /NiS@N-C were gathered by applying aluminum foil as current collector.Meanwhile, coloration that ranges from light purple to red denote a peak intensity characterized by strengthening.Prior to the discharging, as-fabricated Co 3 S 4 /NiS@N-C electrode, depicted in Figure 3E,F Subsequently, the de-intercalation reaction happened as the electrode was further charged from 1.5 to 3.0 V, resulting in the re-formation of the Co 3 S 4 phase corresponding to the (4 0 0) plane at 38.1 • , demonstrating good reversibility of electrochemical reaction for Co 3 S 4 .Notably, the lack of distinct peaks originating from the reformed Na x NiS, Ni 3 S 2 , and NiS at this stage was discovered, which is linked to either their poor crystallinity or the complete covering of the amorphous SEI film on the electrode surface.All these discoveries line up with our prediction of multistep phase-evolution reactions with the intermediate phase generation, and are also compatible with the CV results.Besides, ex situ HRTEM graphs and SAED patterns at four specific voltage points provide additional evidence for these conclusions.Distinctly, the byproduct of the intercalation reaction, that is, Na x Co 3 S 4 , is clearly visible in the HRTEM image (Figure 3G) and corresponding SAED pattern (Figure 3H) after the battery is depleted to roughly 1.0 V, suggesting the good consistency with above ex situ XRD results.Further the voltage decreases to 0.01 V resulted in the labeling of the (1 1 1) plane of Ni/Co together with the (6 1 1) and (2 4 6) planes of Na 2 S at the interplanar spacings of 0.198, 0.216, and 0.256 nm, respectively (Figure 3I).Meanwhile, the distinctive diffraction rings of by-product Na 2 S in the corresponding SAED pattern provide overwhelming support for this (Figure 3J), standing out the occurrence of the conversion reaction.Once the electrode was recharged to 1.6 V, the (1 1 2), (2 4 0), and (2 0 2) planes of Na x Co 3 S 4 are represented by the three nanocrystal regions in the HRTEM image (Figure 3K) with distinct crystal lattices of 0.256, 0.210, and 0.215 nm, respectively.Furthermore, the SAED diffraction spots (Figure 3L) corroborate the presence of Na x Co 3 S 4 nanocrystals, which supports the ex situ HRTEM result.The HRTEM image in Figure 3M validates the lattice distances of 0.238 and 0.297 nm at a fully charged state of 3.0 V, which can be correlated to the (4 0 0) plane of Co 3 S 4 and the (1 0 0) plane of NiS.Correspondingly, three diffraction rings that are indexed to the (2 2 0) and (4 2 2) planes of Co 3 S 4 and (2 2 0) facet of NiS and in the SAED image also manifest the good reversibility of Co 3 S 4 /NiS@N-C composites toward the electrochemical reaction as well as its structural integrity (Figure 3N).A detailed graphical description of Co 3 S 4 /NiS@N-C electrode can be illustrated in Figure 3O based on the above ex situ detection.
To assess the effect of the outer-carbon encapsulation and heterogeneous interface on the electrochemical features of TMCs, the voltage-capacity curves of Co 3 S 4 /NiS@N-C and reference samples, that is, Co 3 S 4 /NiS, Co 3 S 4 , and NiS, are also recorded at 1.0 A g −1 .
In particular, the initial galvanostatic charge/discharge (GCD) profiles for the Co 3 S 4 /NiS@N-C (Figure 4A) present two voltage platforms, which match Na + insertion/extraction and are also in good agreement with the CV results.Meanwhile, the Co 3 S 4 /NiS@N-C electrode provides the remarkable capacities of 903.5 and 829.2 mAh g at the first discharge and charge processes accompanying an initial Coulombic efficiency (ICE) of up to 91.8 %, presenting the remarkable capacity enhancement in contrast with those of Co 3 S 4 /NiS (754.8/731.9mAh g −1 , Figure S11a), Co 3 S 4 (602.8/662.8mAh g −1 , Figure S11b), and NiS (560.7/579.7 mAh g −1 , Figure S11c), further suggesting the improved reaction reversibility and high capacity contribution of Co 3 S 4 /NiS@N-C.Meanwhile, a relatively lower ICE value of Co 3 S 4 /NiS@N-C than other three samples maybe due to the introduction of non-treated carbon source with poor sodium storage ability.Afterward, a remarkable reversible capacity of 705.1 mA h g −1 is maintained after 60 cycles with a capacity retention of 78.0% when the Co 3 S 4 /NiS@N-C electrode was galvanically cycled at 1.0 A g −1 (Figure 4B).In contrast, the reversible capacities for Co 3 S 4 /NiS, Co 3 S 4 , and NiS are only 624.4,537.4,and 508.5 mAh g −1 , respectively.The superiority of Co 3 S 4 /NiS@N-C is further emphasized by its superior rate capability.In especial, the Co 3 S 4 /NiS@N-C electrode at 0.2, 0.5, 1.0, 2.0, 5.0, and 10.0 A g −1 was found to have highly reversible discharge capacities of 747.4,688.9, 643.2, 600.6, 549.0, and 497.8 mAh g −1 (Figure 4C).Surprised, we can observe that even when the electrode cycled at spectacularly 20.0 and 30.0A g −1 , the significantly reversible discharge capacities reaching up to 420.7 and 354.9 mAh g −1 can still be respectively maintained, which can almost reset to the original 755.9 mAh g −1 with the current returns to 0.2 A g −1 , demonstrating the extraordinary rate capability and wonderful structural stability.More interestingly, the Co 3 S 4 /NiS@N-C electrode has a significantly better rate capability, as evidenced by its 1.2, 1.5, and 1.8 times higher reversible capacity at 30.0A g −1 in comparison to the Co 3 S 4 /NiS, Co 3 S 4 , and NiS electrodes.Meanwhile, a comprehensive comparison of specific capacity against the current rate between Co 3 S 4 /NiS@N-C and state-of-art Co 3 S 4 or NiS-based anodes for SIBs was conducted, we can see that the Co 3 S 4 /NiS@N-C electrode stands out on the electrochemical performance among those of SIB anodes (Figure 4D) 18,21,54,55,[60][61][62][63][64][65][66][67][68][69] establishing that the selfconstructed electric field stemmed from the Co 3 S 4 /NiS heterogeneous interface together with the outer-carbon encapsulation on the Co 3 S 4 /NiS nanosphere surface considerably enhance the rate performance reversibility and electrochemical reaction kinetics.Moreover, by graphing the connection between average charge voltage and current rate at a charge potential platform of ∼1.52 V through the GCD curves of four electrodes (Figure S12) at different rates, a comparison of structural pulverization for four electrodes at different rates was conducted.Notably, the Co 3 S 4 /NiS@N-C electrode manifests the lowest polarizability in above-mentioned electrodes (Figure 4E) thanks to a smallest voltage change of only 0.30 V with the current rate increasing from 0.2 to 30.0A g −1 (0.35 V for Co 3 S 4 /NiS, 0.44 V for Co 3 S 4 , and 0.62 V for NiS), standing out its highest electrical conductivity and fastest electron transport.The resistance difference between the electrode and electrolyte was further validated by the electrochemical impedance spectroscopy (EIS) to further account for the reason of increased kinetics behavior of Co 3 S 4 /NiS@N-C.The resulting equivalent circuit is inferred and depicted in the inset of Figure 4F, obviously, a semicircle and an intercept at the real axis denote charge transfer resistance (R ct ) and solvent/ohmic resistance (R s ) in the high-frequency zone, respectively, while Warburg impedance (W) is discernible as a sloping line in the low-frequency range.Through the mentioned equivalent circuit, the Co 3 S 4 /NiS@N-C electrode manifests the smallest R ct and the slope value of Z'∼ ω 1/2 plot (Figure 4G) in four electrodes, meaning its fastest charge-transfer rate and Na + -ion reaction kinetics, as well as highest electronic conductivity in view of the synergistic effect of the constructed Co 3 S 4 /NiS heterostructure and outer-carbon encapsulation.The electrochemical reaction kinetics of as-prepared electrodes is in situ monitored at various discharge-charge phases through exploring the galvanostatic intermittent titration technique (GITT), and a schematic diagram of the GITT calculation and the detailed GITT description is illustrated in Figure S13.Observed from GITT profiles of four electrodes (Figure 4H), the Co 3 S 4 /NiS@N-C electrode affords a smaller overpotential and more remarkable ion-diffusion kinetics in the range of 10 −10 to10 −8 cm 2 s −1 during the whole first discharge-charge cycle (Figure 4I), significantly superior to those of other three electrodes, foreboding faster Na + -diffusion kinetics in Co 3 S 4 /NiS@N-C.The outstanding kinetics feature can be believed to be caused by the stimulation effect on the electron/ion transportation that results from synergistically induced Co 3 S 4 /NiS interfacial interaction and better conductivity of the outer-carbon layer.The ultralong cyclic lifespan of Co 3 S 4 /NiS@N-C was operated under an extremely high current rate of 20.0A g −1 .It is observed in inset of Figure 4J that a discharge-charge process takes only 160.0 s to complete according to the sectional GCD curves of Co 3 S 4 /NiS@N-C electrode at 20.0 A g −1 , and meanwhile, the almost identical outline of the profiles also signifies excellent structural durability and stable electrochemical phase-evolution of Co 3 S 4 /NiS@N-C.Particularly as evidence of exceptional cycling stability, the Co 3 S 4 /NiS@N-C maintains an appealing discharge capacity reaching 310.3 mAh g −1 with an extremely small capacity fading of only 0.05% each cycle even after 2 400 cycles, which significantly outperforms the previous Co 3 S 4 or NiS-based anodes (Table S1), verifying its extraordinary cycling stability and superior reversibility.
To systematically shed light on the inherent difference and origin in high-rate capabilities of four electrodes, the electrochemical reaction kinetics characteristics in the discharge-charge processes were thoroughly examined by separating the charge-store mechanisms induced by the surface-capacitive and diffusion behaviors with the use of CV at various scan rates, varying from 0.2 to 2.0 mV s −1 .One can observe that the CV curves of each electrode show nearly the same profile outlines and variation tendency at different scan rates, and meanwhile their redox peaks are well conserved even at a high rate of 2.0 mV s −1 (Figure 5A and Figure S14a,d,g), revealing the rapid and reversible electrochemical process without a noticeable phase transition. 19Simultaneously, it is readily apparent that, as the scan speed increases, the peaks move toward a higher potential, whereas the cathodic peaks underwent a decrease in potential.The sustainable shift of redox peaks in the opposite direction illustrates the weak polarization of the electrode in the electrolyte and the presence of combined diffusion-controlled and surface capacitive behaviors. 70The connection between peak current (i) and scan rate (v) can be used to determine whether the current is regulated by an ion-diffusion reaction or a pseudocapacitive-controlled reaction. 5,12

𝑖 = 𝑎𝑣 𝑏
(1) Specifically, the b value, the fitted slope of the log(i) vs. log(ν) plot, holds significance since it stands for the rate-controlling factor of Na + insertion/de-insertion.Normally, the b value approaching 0.5 often indicates an ion diffusion-controlled process, whereas it that gets closer to 1.0 signifies a capacitive mechanism with a rapid reaction kinetic for Na + -storage.As for the calculated results for Co 3 S 4 /NiS@N-C depicted in Figure 5B, the b values at three redox peaks, which fall between 0.5 and 1.0, illustrate two mechanisms work together to synergistically produce the exceptional electrochemical performance.For the purpose of being able to conduct a quantitative analysis of the contribution to the capacity at each course, the diffusioncontrolled feature and the surface-capacitive reaction were achieved by establishing the current i at a stationary potential V as follows: 35,40 One could separate the capacitive process by computing the k 1 and k 2 constants as the current percentage increases during the Na + -ion diffusion. 39The surface-capacitive contributions of Co 3 S 4 /NiS@N-C, Co 3 S 4 /NiS, Co 3 S 4, and NiS are produced to be about 78.4%, 82.3%, 83.7%, and 84.1% at 0.2 mV s −1 , respectively.Subsequently, their capacitive contributions gradually develop up to 95.3%, 94.6%, 94.2%, and 92.1% as the scan rate increases to 2.0 mV s −1 , and the typical voltage profiles for computed surface-capacitive current related to the tested current are also exhibited by the shaded area (Figure 5C and Figure S12c,f,i).Significantly, the capacitive contributions of Co 3 S 4 /NiS@N-C are greater than those of other three electrodes at all scan rates (Figure 5D).Undoubtedly, a greater proportion of the pseudocapacitive contribution may facilitate faster Na +ion transmission and reaction dynamics, hence enhancing the rate capability of Co 3 S 4 /NiS@N-C, which are advantageous due to the conductive outer-carbon skeleton and abundant heterogeneous interface.The evolution of reaction kinetics for the Co 3 S 4 /NiS@N-C electrode under the cycling were estimated with the aid of the EIS spectra test, as depicted in Figure 5E.The initial wetting and activation of Co 3 S 4 /NiS@N-C electrode is mostly responsible for the decline in R ct during the first 15 cycles. 71But as the cycle goes on from 15th to 50th, the R ct steadily increases, attributable to the structural pulverization and the reduplicative manufacturing of the instability SEI layer. 72king into account the impressive electrochemical capabilities in the half-cell, the usage possibilities of asprepared Co 3 S 4 /NiS@N-C were assessed by fabricating sodium-ion full cells (SIFCs), which are packaged by using preactivated Co 3 S 4 /NiS@N-C electrode as the anode and Na 3 V 2 (PO 4 ) 3 @C (NVP@C) as the cathode to construct a Co 3 S 4 /NiS@N-C//NVP@C SIFCs.Concurrently, Figure 5F manifests a diagrammatic representation of the working mechanism for Co 3 S 4 /NiS@N-C//NVP@C SIFCs during the charging-discharging processes.Meanwhile, the phase component and electrochemical capability of NVP@C are illustrated in Figures S15 and S16.It is evident that NVP@C electrode achieves superior Na + -storage features involving attractive capacity and impressive cycle durability in a half cell system.As depicted in Figure 5G, the GCD profiles of Co 3 S 4 /NiS@N-C//NVP@C SIFCs with a voltage range from 0.4 to 4.0 V support the appealing capacities of about 641.4 and 627.3 mAh g −1 at the initial discharge and charge processes at 1.0 A g −1 , respectively, affording an outstanding ICE of 97.8%, and then the coulombic efficiency increases rapidly to nearly 100% and stays there for the duration of the following cycles.Meanwhile, a pair of charge/discharge platforms, centered at around 3.5/3.1 V, are what draw particular attention to the first GCD curves, which can be divided into two pairs (3.3/2.4 and 3.5/21.6V) beginning with the second cycle.Even after withstanding 60 consecutive loops (Figure 5H), the SIFCs still provide the significant reversible capacity, with the values of approximately 407.9 mAh g −1 at 1.0 A g −1 and 315.1 mAh g −1 at 5.0 A g −1 .Notably, the successful usage of the charged coin-type SIFCs to illuminate commercial light-emitting diode (LED) lights screen displayed with the word "SIBs" (inset of Figure 5H) is impressive and offers a great deal of potential for the practical application sustainability of Co 3 S 4 /NiS@N-C for portable consumer electronics.The remarkable rate performance of SIFCs was also demonstrated in Figure 5I,J, which yields reversible capacities of 624.8, 578.2, 503.6, 455.91, 386.0, and 305.1 mAh g −1 for current rates of 0.2, 0.5, 1.0, 1.5, 3.0, and 5.0 A g −1 in that sequence.Subsequently, the reversible capacity immediately changes to 532.5 mAh g −1 , once the rate resets to 0.2 A g −1 , producing a superior capacity retention of up to 85.2%.Generally, the different mass ratios between anode and cathode have an important influence on the electrochemical performance of full cells.Therefore, we adjusted the capacity ratio between the anode and cathode to explore the important influence on the electrochemical performance of full cells, the corresponding result is shown in Figure S18a.It is found that the Co 3 S 4 /NiS@N-C//NVP@C SIFCs delivers the initial discharge and charge capacities of 533.9 and 529.3 mAh g −1 at 1.0 A g −1 , when the ratio of anode to cathode is about 1:3.With the cycling progresses to the 60th cycle, the full cell obtains a reversible capacity of 386.2 mAh g −1 (Figure S18b).As the mass ratio between the anode and cathode increases to 1:5, the initial discharge and charge capacities of full cell are about 480.1 and 517.2 mAh g −1 at 1.0 A g −1 (Figure S18c), subsequently, a reversible discharge capacity of 257.mAh g −1 can be harvested after 60 cycles (Figure S18d).These results are obviously smaller than that of the full cell with the ratio of anode to cathode electrode of 1:4, confirming that the optimal ratio between anode and cathode is about 1:4.
In addition, we also integrated a commercial activated carbon (AC) cathode and preactivated Co 3 S 4 /NiS@N-C anode to create asymmetrical Co 3 S 4 /NiS@N-C//AC sodium ion hybrid capacitor (SIHCs) device that could further demonstrate the advantageous properties of heterostructure engineering in terms of electron and Na + -ion transport capability.Correspondingly, AC cathode, as illustrated in Figure S17, manifests remarkable electrochemical performance, featuring a good cyclic capability over 150 cycles at 0.1 A g −1 .The SIHCs are capable of operating continuously at an operating voltage of 0.01-4.2V, and their CV profiles exist a slight deviation relative to the ideal rectangular shape (Figure S19a), which could be attributed to the various types of the charge storage mechanism between anode and cathode electrodes. 73Meanwhile, more evidences from CV curves under various scan rates illustrate that the capacitive-controlled behavior drive the Na + -storage mechanism. 74Interestingly, even with a 60fold increase in scan rate, the outlines of CV profiles essentially stay constant without encountering substantial distortion, proving the great rate capacity and superb reversibility.Similarly, the quasitriangular-shaped GCD curves at the current rate between 0.1 and 2.0 A g −1 reflect a capacitive-dominated charge storage mechanism (Figure S19b).Additionally, the energy/power densities of SIHCs device are computed according to the GCD curves.Ragone plots of Co 3 S 4 /NiS@N-C//AC SIHCs based on the total mass of both electrodes in Figure S19c illustrate that the SIHCs device features the superior gravimetric energy densities of 150.6/18.6Wh kg −1 at the gravimetric power densities of 210/3 150 W kg −1 , respectively.The evaluation of cycle durability is presented in Figure S19d.After 300 cycles, the Co 3 S 4 /NiS@N-C//AC SIHCs device is able to keep 96.3% of its initial capacitance at a current rate of 0.5 A g −1 , as well as nearly 100% CE, proving its outstanding cycling stability and potential use in future practical applications.
The main goal of the density functional theory (DFT) computation is to investigate the significance of constructing a strongly coupled heterointerface structure on superior electrochemical Na + storage performance.The correspondingly optimized Co 3 S 4 /NiS, Co 3 S 4 , and NiS structural configurations are potted in Figure S20.According to the associated density of states (DOS) in  6D, which suggest the obvious charge transfer between Na atom and three models.The accumulation of electron surrounding the Co 3 S 4 /NiS and the electron depletion of Na atom is visible.Meanwhile, a higher interaction occurs in the region between Na + and Co 3 S 4 /NiS compared to the Co 3 S 4 -Na, and NiS-Na models, suggesting that Na + is more easily absorbed on the rich heterogeneous interface and synergistically promotes the Na + -storage performance.Bader charge analysis suggests that 0.823e, 0.819e, and 0.788e electrons are respectively transferred from Na atom to Co 3 S 4 /NiS, Co 3 S 4 , and NiS models.Obviously, the stronger charge transfer means a more significant Na + adsorption, which agrees well with some previous study. 30Moreover, the Na + -adsorption binding energies (E abs ) and the corresponding absorption configurations are manifested in Figure 6E.The E abs values are −1.89,−1.35, and −0.89 eV for the Co 3 S 4 /NiS, Co 3 S 4 , and NiS, respectively.Obviously, the Co 3 S 4 /NiS shows the strongest Na + -ion adsorption among three structural models, which usually means its more favorable adsorption sites and better reaction kinetics.It is evident that all the computed results back up the experimental result that the formation of Co 3 S 4 /NiS heterointerface can significantly enhance the electronic conductivity and Na +adsorption ability of TMCs, thereby endowing the superior electrochemical Na + -storage performance.

CONCLUSIONS
In summary, we developed an easy protocol for the design of a hierarchically hybrid material comprising hetero-Co 3 S 4 /NiS hollow nanosphere encapsulated within an ultrathin N-doped carbon matrix (Co 3 S 4 /NiS@N-C) through vulcanization, in situ dopamine polymerization, and carbonization using CoNi-glycerate as the template.The well-designed Co 3 S 4 /NiS@N-C architecture simultaneously integrates numerous merits including fast ion-diffusion and charge-transfer kinetics, superior ), Chongqing Talent Innovation and Entrepreneurship Team Project (CQYC202203091274).In addition, the authors would like to thank Shiyanjia Lab (http://www.shiyanjia.com) for the XPS and TEM analysis.

C O N F L I C T O F I N T E R E S T S TAT E M E N T
The authors declare no conflict of interest.

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I G U R E 1 (A) Detailed diagram of the synthetic routes of heterogeneous Co 3 S 4 /NiS@N-C composites.FESEM and TEM images at different magnifications for the samples: (B-E) CoNi-glycerate solid nanospheres, (F-J) hollow Co 3 S 4 /NiS@N-C nanospheres.(K) HRTEM graph with the matching line scan intensity profiles, (L) SAED pattern, and (M) EDX elemental mappings of Co 3 S 4 /NiS@N-C composites.FESEM, Field-emission scanning electrode microscopy; TEM, transmission electron microscopy; SAED, selected area electron diffraction.

0 2 )
planes of NiS together with the (2 2 0), (3 1 1), and (4 0 0) planes of Co 3 S 4 .An additional indication of the co-existence of Co 3 S 4 and NiS in the heterogeneous Co 3 S 4 /NiS@N-C composites is provided by Figure 1M, where the high angle annular dark field (HAADF) TEM imaging and associated energy-dispersive X-ray spectroscopy (EDX) elemental mapping analysis clearly reveal that the distribution outlines of Co, Ni, S, C, and N elements continue to be the envisioned geometric microstructure of each nanosphere.As comparison, bare Co 3 S 4 and NiS hollow nanospheres can be obtained through directly vulcanizing Co-G and Ni-G nanospheres through hydrothermally induced chemical etching.One can see that the Co 3 S 4 sample keeps almost the same spherical structure as Co-G nanospheres but has a rougher surface (Figure S7a,b).

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I G U R E 3 (A) CV curves at 0.5 mV s −1 of Co 3 S 4 /NiS@N-C.Ex situ high-resolution XPS spectra at different initial discharge-charge states: (B) Co 2p, (C) Ni 2p, and (D) S 2p.(E,F) Ex situ XRD patterns at different initial discharge-charge states.Ex situ HRTEM and SAED patterns at discharged states of (G,H) 1.0 V, (I,J) 0.01 V, and charged states of (K,L) 1.60 V, (M,N) 3.0 V. (O) The graphical illustration of phase-transformation of Co 3 S 4 /NiS@N-C.CV, Cyclic voltammetry; XPS, X-ray photoelectron spectroscopy; XRD, X-ray diffraction; SAED, selected area electron diffraction.
, is clearly capable of detecting the Co 3 S 4 peaks at 26.7 • , 31.4 • , 38.1 • , 50.2 • , and 55.0 • together with NiS peaks at 30.2 • , 34.7 • , 46.1 • , and 53.5 • , these signals exhibit a slight migration toward a lower 2θ owing to the crystal lattice expansion resulting from the intercalation of Na + into Co 3 S 4 /NiS, followed by the gradual disappearance.Meanwhile, a new reflection signal emerged at about 16.0 • , attributable to the (1 1 0) of intermediate Na x Co 3 S 4 (JCPDS #79-2145), represents the occurrence of the intercalation reaction when the electrode was discharged to 1.0 V.There is the noticeable color increase at 19.1 • , 31.6 • , and 34.7 • that are indexed to the (2 2 2), (4 0 4), and (6 1 1) facets of Na 2 S (JCPDS #47-0178) and is caused by the conversion reaction from the Na x Co 3 S 4 /Na x NiS phase to Fe/Ni and Na 2 S phases as the potential drops to 0.01 V. Following the charging process, the Na x Co 3 S 4 reflections with the (1 3 0) facet at 27.6 • and (2 2 0) facet at 32.3 • emerge in tandem with the gradual weakening and final vanishing of the Na 2 S phase with the charging process continues to 1.6 V, further revealing the reversible transformation process of Fe/Ni and Na 2 S to Na x Co 3 S 4 /Na x NiS phases.

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I G U R E 4 (A) Discharge-charge curves of Co 3 S 4 /NiS@N-C at 1.0 A g −1 .(B) Cycling stability at 1.0 A g −1 and (C) rate features in a rate range of 0.2∼30.0A g −1 of Co 3 S 4 /NiS@N-C together with other three reference samples.(D) Comparison of rate capability with other reported state-of the-art Co 3 S 4 and NiS-based anodes.(E) Relationship between average charge working voltage of 1.52 V and current rate for the Co 3 S 4 /NiS@N-C together with other three reference samples.(F) EIS spectra, (G) Warburg impedance coefficients stemmed from the linear relationship between Z′ and ω −1/2 , (H) GITT potential profiles, and (I) calculated Na + -diffusion coefficients of Co 3 S 4 /NiS@N-C together with three reference samples.Inset shows partial GCD curves of Co 3 S 4 /NiS@N-C at 20.0 A g −1 .EIS, Electrochemical impedance spectroscopy; GITT, galvanostatic intermittent titration technique; GCD, galvanostatic charge/discharge.

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I G U R E 5 (A) CV curves of Co 3 S 4 /NiS@N-C in a scan rate range of 0.2-2.0 mV s −1 .(B) Fitting lines of log v and log i at different redox peaks, (C) Separation of capacitive and diffusion contribution at 2.0 mV s −1 .(D) Comparison of the capacitive contribution for four samples at different scan rates.(E) EIS spectra of Co 3 S 4 /NiS@N-C at diverse cycles.(F) The working mechanism diagram of Co 3 S 4 /NiS@N-C//NVP@C SIFCs device.(G) GCD profiles at 1.0 A g −1 , (H) cycle stability at 1.0 and 5.0 A g −1 , (I) GCD profiles in a rate range of 0.2-5.0A g −1 , and (J) rate performance of Co 3 S 4 /NiS@N-C//NVP@C SIFCs device.CV, Cyclic voltammetry; EIS, electrochemical impedance spectroscopy; SIFC, sodium-ion full cell; GCD, galvanostatic charge/discharge.

Figure
Figure 6A-C, one can see that all these models reveal outstanding metallicity characteristic with the electron states cross the Fermi level.Especially, the Co 3 S 4 /NiS model presents the highest electron state at the Fermi level, thus signifying that the Co 3 S 4 /NiS may possess a higher electronic conductivity in comparison to that of Co 3 S 4 and NiS.The charge density difference of Co 3 S 4 /NiS shown in Figure S21 reveals the intense charge transfer and exchange around the Co 3 S 4 /NiS heterointerface, which can facilitate the adsorption and migration of Na +ion.Additionally, the adsorbed Na + bonding features on Co 3 S 4 /NiS, Co 3 S 4 , and NiS configurations (denoted as Co 3 S 4 /NiS-Na, Co 3 S 4 -Na, and NiS-Na) are also uncovered through charge density difference analysis, as illustrated in Figure6D, which suggest the obvious charge transfer between Na atom and three models.The accumulation of electron surrounding the Co 3 S 4 /NiS and the electron depletion of Na atom is visible.Meanwhile, a higher interaction occurs in the region between Na + and Co 3 S 4 /NiS compared to the Co 3 S 4 -Na, and NiS-Na models, suggesting that Na + is more easily absorbed on the rich heterogeneous interface and synergistically promotes the Na + -storage performance.Bader charge analysis suggests that 0.823e, 0.819e, and 0.788e electrons are respectively transferred from Na atom to Co 3 S 4 /NiS, Co 3 S 4 , and NiS models.Obviously, the stronger charge transfer means a more significant Na + adsorption, which agrees well with some previous study.30Moreover, the Na + -adsorption binding energies (E abs ) and the corresponding absorption configurations are manifested in Figure6E.The E abs values are −1.89,−1.35, and −0.89 eV for the Co 3 S 4 /NiS, Co 3 S 4 , and NiS, respectively.Obviously, the Co 3 S 4 /NiS shows the strongest Na + -ion adsorption among three structural models, which usually means its more favorable adsorption sites and better reaction kinetics.It is evident that all the computed results back up the experimental result that the formation of Co 3 S 4 /NiS heterointerface can significantly enhance the electronic conductivity and Na +adsorption ability of TMCs, thereby endowing the superior electrochemical Na + -storage performance.

F I G U R E 6
DOS of (A) Co 3 S 4 /NiS, (B) Co 3 S 4 , and (C) NiS models.(D) Charge density difference of Co 3 S 4 /NiS, Co 3 S 4 , and NiS with one Na atom adsorption.The yellow and cyan regions denote the gain and loss of electrons, respectively.(E) Structural models of Co 3 S 4 /NiS, Co 3 S 4 , and NiS with one Na adsorption and matched Na + -adsorption energy.DOS, Density of states.electricconductivity, abundant Na + -transport channels, good structural stability, and adequate active reaction sites, thereby giving the constructed Co 3 S 4 /NiS@N-C-based batteries a significantly more desirable initial reversible capacity, rate capability, and cycling stability as comparison to other three reference samples.More specifically, the Co 3 S 4 /NiS@N-C electrode affords appealing discharge capacity reaching 310.3 mAh g −1 with an extremely small capacity fading of only 0.05% each cycle even after 2 400 cycles.Ex situ XRD together with ex situ XPS and TEM characterizations verified the insertion-conversion mechanism and strong reversibility of Co 3 S 4 /NiS@N-C.Additionally, the SIFC and hybrid capacitor combined with an NVP@C or AC cathode and Co 3 S 4 /NiS@N-C anode exhibits good electrochemical characteristics, such as exceptional rate capability, impressive cycle stability, and specific capacity, showcasing the outstanding feasibility for practical use.According to the DFT calculation, the favorable electrochemical features of Co 3 S 4 /NiS@N-C were associated with its high conductivity and excellent Na + -adsorption ability upon cycling process.This study not only offers a unique viewpoint on the usage of heterogeneous metal sulfides in high-efficiency Na + -storage fields, but also overcomes the structural instability and slow reaction kinetics that frequently exists in SIBs systems.A C K N O W L E D G M E N T SThis work was supported by Natural Science Foundation of Chongqing (Nos.CSTB2022NSCQ-MSX0798 and CSTB2023NSCQ-MSX0371), Natural Science Foundation of Sichuan (No. 24NSFSC1052), Science and Technology Research Program of Chongqing Municipal Education Commission (No. KJQN202101439 and No. KJQN202101441), Youth Science and Technology Foundation of Gansu Province (Grant number: 21JR1RA320), Cooperative Projects between Undergraduate Universities in Chongqing and Institutes affilated with Chinese Academy of Science (HZ2021014), Key Projects of Technological Innovation and Application Development in Chongqing (2022TIAD-KPX0159 • , 31.4 • , 38.1 • , 50.2 • , and 55.1 • .While the additional peak signals appearing at 30.2 • , 34.7 • , 46.1