摘要：銻（Sb），因其具有較高的理論比容量（660 mAh?g?1）、較低儲鈉電位（0.5–0.8 V vs. Na/Na+）和較高的密度（6.68g?cm?3）等特點，被認(rèn)為是一種理想的鈉離子電容器的陽極材料。然而，在Na+脫嵌過程中，Sb電極會發(fā)生較大的體積變化，導(dǎo)致其容量快速衰減以及倍率性能變差，阻礙了Sb電極的實際應(yīng)用。因此，本文提出一種可用于制備錨定在具有碳涂層的二維石墨烯表面的無定型Sb納米顆粒的電化學(xué)置換方法。所制備Sb/石墨烯復(fù)合材料具有典型的二維復(fù)合結(jié)構(gòu)，可大幅增加與電解液界面接觸面積，縮短離子擴散路徑，促進離子遷移與電子轉(zhuǎn)移。進一步利用該復(fù)合材料作為陽極，自制活性炭作為陰極，構(gòu)建出一種新型鈉離子電容器。研究證實，該鈉離子電容器工作電壓可達4.0 V，可輸出140.75Wh?kg?1的最大能量密度和12.43 kW?kg?1的最高功率密度。綜上，該研究結(jié)果可為鈉離子儲能器件用高容量銻基陽極材料的優(yōu)化設(shè)計提供可借鑒的思路。

關(guān)鍵詞：石墨烯；銻基陽極；電化學(xué)置換反應(yīng)；二維復(fù)合材料；鈉離子電容器

中圖分類號：O646

Galvanic Replacement Synthesis of Graphene Coupled Amorphous Antimony Nanoparticles for High-Performance Sodium-Ion Capacitor

Abstract： Sodium-ion energy storage devices are considered as an idealsubstitute for popular lithium-ion counterparts because of its resource richnessand environmental friendliness. Among the various sodium-ion energy storagedevices， sodium-ion capacitors （SICs） have the combined advantages in highenergy and power densities as well as long-term cycling stability in theory.Antimony （Sb） is considered as an attractive anode material for SICs due to itshigh theoretical capacity of 660 mAh?g?1， low operating potential （0.5–0.8 V vs.Na/Na+）， and high density of 6.68 g?cm?3. However， the large volume changeof Sb during the Na+ insertion leads to fast decay in capacity and poor ratecapability， which becomes a fundamental issue greatly hindering the practicalapplication. Herein， a facile galvanic replacement approach is proposed for the synthesis of an ultrafine amorphous Sbnanoparticles anchoring on carbon coated two-dimensional （2D） reduced graphene oxides （RGO）. Half-cell test （vs. metalNa） shows that as-prepared Sb-C@RGO anode delivers a high specific capacity of 521.5 mAh?g?1 at 0.1 A?g?1. As thecurrent density increases to 10 A?g?1， Sb-C@RGO anode still maintains a specific capacity of 83.5 mAh?g?1， suggesting itshigh-rate properties. The excellent Na+ charge storage property of Sb-C@RGO anode is primarily due to its unique 2Dhybrid architecture， which largely increases the atomic interface contact with Na+ and shortens ion diffusion path， thusfacilitating ion/electron transfer. To demonstrate the feasibility of Sb-C@RGO as the high-performance electrode foremerging energy-storage devices， a hybrid cell configuration （e.g.， SIC） was fabricated by employing the Sb-C@RGO asthe negative electrode （battery type） and home-made activated carbon （PDPC） as the positive electrode （capacitive type）in a Na+ based organic electrolyte. This SIC is capable of operating at a high voltage of 4.0 V and exhibiting a high energydensity of 140.75 Wh?kg?1 at a power density of 250.84 W?kg?1. Even the power density is magnified ～50 times to 12.43kW?kg?1， this SIC still delivers a high energy density of 55 Wh?kg?1. Within a short charge/discharge of ～3.2 min， this SICcan store/release quite a high energy density of 108.5 Wh?kg?1， which represents the remarkable performance among thereported Sb-based capacitors. In addition， this SIC shows the good cycling stability with an acceptable capacity retentionvalue of 66.27% after 1000 cycles at a current density of 2 A?g?1. Our results may provide insight into the rational designand construction of high-capacity Sb-based anode materials for advanced sodium-ion based energy storage devices.

Key Words： Graphene; Sb anode; Galvanic replacement reaction; 2D composite; Sodium-ion capacitor

1 Introduction

Sodium-ion energy storage devices， as the promisingalternatives for popular lithium-ion counterparts， have attractedwidely attention because of the nature abundance in earth’s crust（23600 mg?L?1）， low cost， and environmental benignity ofsodium resources 1–3. Among the various sodium-ion energystorage devices， sodium-ion capacitors （SICs）， consisting ofbattery-type negative electrode and capacitive positive carbonelectrode， in theory， have the combined advantages in highenergy and power densities as well as long-term cyclingstability 4–6. However， most of reported SICs performed belowexpectation on energy and/or power densities. That is mainlybecause of most of anode materials cannot fully accommodatethe large size of Na+， leading to the sluggish diffusion kinetics，then accelerating the kinetics mismatch between batter-typeanode and capacitive cathode 7–9. Therefore， exploring suitableelectrode materials with reversible， robust， and fast Na+ chargestorage properties remain a challenge.

Currently， various anode nanomaterials includingintercalation-type， redox-type， and alloy-type materials havebeen explored to solve the above-state issue for SICs 10–17.Among them， antimony （Sb） with its high theoretical capacity of660 mAh?g?1， safe operating potential （0.5–0.8 V vs. Na/Na+），and high density of 6.68 g?cm?3 11，18，19， is considered to be one ofthe most promising anodes for high-performance SICs.However， the large volume change （over 300%） during sodiationleads to large capacity decay and poor rate capability 20， whichgreatly hinders the practical application. To circumvent thisissue， various strategies have been developed to improve theelectrochemical performance of Sb anodes， such as reducing thesize into nanoscale 21，22， creating nanoporous structure 23–26， andemploying carbonaceous materials as the buffer layer 27，28.Among these strategies， integrating nanosized Sb into carbonframeworks including one-dimensional （1D） nanofibers， twodimensional（2D） carbon sheets， and three-dimensional （3D）carbon microstructures through electrospinning technique，hydrothermal method， spray-drying processing， etc. 21，29–34， hasbeen demonstrated to be the most effective way to accommodatethe large volume expansion and improve the electronicconductivity. As expected， both the rate capability and thecycling capability of Sb-carbon anodes were largely improved.Therefore， it is highly desired to explore more feasible strategiesto fabricate Sb-carbon composite electrodes with reversible，robust， and fast Na+ charge storage properties to meet therequirement from the high-performance SICs.

Herein， we report a facile galvanic replacement approach toprepare amorphous Sb nanoparticles-reduced graphene oxides（Sb-C@RGO） composite. The Sb-C@RGO composite displaysthe attractive Na+ charge storage performance， which can be usedas an anode for high-performance SIC.

2 Experimental section

2.1 Chemicals

All chemicals were of analytical grade and used directlywithout further purification. CoSO4?7H2O， NiSO4?6H2O，ammonium hydroxide， dopamine， tris（hydorxymethyl）aminomethane and SbCl3 were purchased from AladdinBiochemical Technology. All chemicals were used as receivedwithout further purification.

2.2 Synthesis of NiCo hydroxide nanosheets ongraphene （NiCo-HNS@GO）

Graphene oxide （GO） was synthesized by a modified Hummermethod. CoSO4?7H2O （1.124 g， 4 mmol） and NiSO4?6H2O（0.526 g， 2 mmol） were dissolved in 30 mL distilled water to form pink solution. Then the pink solution was added to thesuspension of GO solution （1 mg?mg?1， 80 mL） under stirring，and 5 mL of ammonium hydroxide was added dropwise using aseparatory funnel and stirred for 5 min. Then the mixture wassonicated in a beaker for 30 min to form a brown suspension.The products were collected by centrifugation at 8000 r?min?1for 10 min. The obtained NiCo-HNS@GO was washed threetimes with ethanol and distilled water. After that， NiCo-HNS@GO powder was dried in a freeze dryer for 24 h.

2.3 Synthesis of polydopamine coated NiCo-HNS@GO （PDA@NiCo-HNS@GO）

As-prepared NiCo-HNS@GO powder （100 mg） wasdispersed in the mixed solution of 80 mL ethanol and 30 mLdistilled water and stirred at 500 r?min?1 for 30 min. Then，tris（hydroxymethyl） aminomethane （0.484 g） dispersed in 40mL distilled water and dopamine （60 mg） dissolved into 30 mLwere added into the above solution in sequence. After that， themixture was stirred at room temperature of 100 r?min?1 for 24 h.The products were collected by centrifugation at 8000 r?min?1for 10 min and then washed three times with ethanol and distilledwater. The achieved products were dried in a freeze dryer for 24h to obtain the PDA@NiCo-HNS@GO powder.

2.4 Synthesis of carbon coated Ni-Co nanoparticlesloading on reduced GO （Ni-Co-C@RGO）

Ni-Co@RGO was synthesized by a pyrolysis process.PDA@NiCo-HNS@GO power （200 mg） was put into porcelainboat and then heated at 800 °C for 1 h under Ar atmosphere witha heating rate of 5 °C?min?1. Finally， black Ni-Co-C@RGOsample was collected after cooling to room temperature.

2.5 Synthesis of carbon coated Sb nanoparticlesloading on RGO （Sb-C@RGO）

Ni-Co-C@RGO （100 mg） and SbCl3 （0.26 g） were mixed in60 mL ethanol， and ultrasonically treated in a beaker for 30 minto form a blue suspension. Then， the above solution wastransferred to a 100 mL Teflon-lined stainless-steel autoclaveand heated at 100 °C for 24 h. After cooling to room temperature，the products were collected by centrifugation at 8000 r?min?1 for10 min. The obtained Sb-C@RGO was washed several timeswith ethanol and distilled water. After that， Sb-C@RGO weredried in a freeze dryer for 24 h. For comparison， Sb@RGO wasobtained under the same experimental procedures， except forPDA coating.

2.6 Materials characterization

The structure and composition of samples were studied byPower X-ray diffraction （XRD， DMAX-2500PC， Japan） usingCu-Kα radiation. Field-emission scanning electron microscopy（FESEM， JSM-7800F， JEOL， Japan） and transmission electronmicroscopy （TEM， JEM-F200， JEOL， Japan） were employed toprobe the morphology and structure of the samples. Ramanspectra of the samples were achieved by a Raman spectroscope（JY-HR800， excitation wavelength of 532 nm， France）. X-rayphotoelectron spectroscopy （XPS， AXIS Supra， UK） was usedto obtain the surface chemical species of the samples. Thesurface area and pore-size distribution of the samples werestudied by an ASAP2020 volumetric adsorption analyzer（Micromeritics， USA） at 77 K. The mass loading of Sb incomposite was investigated by Thermogravimetry （TGA） onPerkinElmer （TGA8000， USA） with an elevated temperaturewith heating rate of 10 °C?min?1.

2.7 Fabrication of half-cell and full-cell configurations

The electrochemical properties of the Sb-C@RGO sampleswere evaluated through a half-cell configuration and a full-cellconfiguration. The working electrode was prepared by casting aslurry of active materials， carbon black， and polyvinylidenefluoride （PVDF） with a mass ratio of 7 ： 2 ： 1 on a copper foiland drying under vacuum at 80 °C for 10 h. The methyl-2-pyrrolidone （NMP） was added to assist to form a slurry. Thecopper foil coated with electrode materials was punched intoround electrode with a diameter of 12 mm. The mass loading ofthe active material on the electrode was 1 mg?cm?2. For thefabrication of half-cell， the metal Na foil （worked as the counterand reference electrodes）， glass fiber separator and Sb-C@RGOelectrode were put into a coin type cell （2032 type） in sequence.Then， 80 μL of 1 mol?L?1 NaClO4 （ethylene carbonate/dimethylcarbonate/ethyl methyl carbonate （EC/DMC/EMC） volume ratiois 1 ： 1 ： 1， 5.0% fluoroethylene carbonate （FEC）） was added.After that， the half-cell was sealed by a sealing machine. Beforethe full-cell fabrication， the Sb-C@RGO negative electrodeneeded a presodiated process. Typically， the Sb-C@RGOelectrode was cycled in a half cell for 5 cycles under a chargedischargecurrent density of 0.05 A?g?1， ended at a sodiated state（at 0.01 V）， and then detached in an Ar-filled glovebox. Duringthe full-cell fabrication， the home-made polyaniline-derivedporous carbon （PDPC） positive electrode replaced metal Naelectrode. More details about the PDPC electrode can be seen inthe previous works 35. Herein， the active mass ratio between theSb-C@RGO and PDPC is 1 ： 1 during the cell assembly.

2.8 Electrochemical measurements

The electrochemical workstations （IVIUMnSTAT， IviumTechnologies BV， The Netherlands and CHI760e， ShanghaiChenhua， China） were used to record the cyclic voltammetry（CV） curves and galvanostatic intermittent titration technique（GITT） curves. A battery test instrument （Land CT2001A，Wuhan Land Electronics. Ltd.） was employed to record thecapacities and coulombic efficiencies during the differentcurrent densities and long-term cycling tests.

3 Results and discussion

Fig. 1 schematically illustrates the whole fabrication processof two-dimensional （2D） Sb-C@RGO sheets. Typically， thehigh-density individual Ni-Co hydroxide nanosheets arehomogeneously grown on GO sheets （denoted as NiCoHNS@GO） by a coprecipitation method 36， as confirmed by theSEM and TEM images （Figs. S1 and S2， SupportingInformation）. An ultrathin polydopamine （PDA） layer was thencoated on the NiCo-HNS@GO composites， as evidenced by thicker Ni-Co hydroxide nanosheets shown in SEM （Fig. S1）and TEM （Figs. S1 and S3） images. After pyrolysis at 800 °C，the Co-Ni hydroxide nanosheets are transformed into CoNi alloynanoparticles with an average size of 23.50 nm which arehomogenously dispersed on reduced graphene oxide （RGO）nanosheets （denoted as NiCo@RGO） （Figs. S1 and S4）.Afterward， NiCo@RGO served as a structural template， and theNiCo nanoparticles were in situ substituted by Sb nanoparticlesthrough a galvanic replacement reaction to obtain Sb-C@RGOsample （Fig. 2a，b） 20，36，37. High-resolution TEM images （Fig. 2c），selected area electron diffraction （SAED） （Fig. 2d） and energydispersiveX-ray spectroscopy （EDX） elemental mappingimages （Fig. 2e–i） show that amorphous Sb nanoparticles werehomogenously dispersed on RGO sheets. During the synthesizedprocedure， the introduced PDA layer can be carbonized intocarbon network， which plays a role in anchoring Ni-Conanoparticles onto RGO sheets homogenously， which is consistentwith other observation 36，37. Well-dispersed Ni-Co nanoparticles ishelpful to obtain small-sized Sb nanoparticles. Without PDAcoating， large and irregular Sb nanoparticles were formed （denotedas Sb@RGO， Figs. S5 and S6）.

XRD pattern of Sb-C@RGO composite in Fig. 3a shows twobroad diffraction peaks around 28.2° and 54.7°， which suggeststhat Sb-C@RGO composite is mainly composed by amorphouscarbon （or graphene shown in Fig. S7） and amorphous Sb and/orultra-small Sb nanocrystals. The amorphous and/or ultrasmallproperty of Sb are consistent with HRTEM observation andelectron diffraction （ED） pattern （Fig. 2d）. For comparison，Sb@RGO shows the strong diffraction peaks （36.5°， 42.5°，44.3°， 51.6°， 61.6°， and 76.0°） assigned to Ni （JCPDS No. 87-0712） and CoO （JCPDS No. 75-0533） and weak diffraction peak（28.4°） assigned to Sb （JCPDS No. 71-1173）. The diffractionpeaks of Ni and CoO suggest that Ni-Co nanoparticles are notfully substituted by Sb. Fig. 3b shows the Raman spectra for Sb-C@RGO which has two broad disordered induced D-bands andin-plane vibration G-bands at round 1344 and 1578 cm?1，respectively， suggesting the lower degree of graphitic orderingof RGO substrate. For the Sb@RGO sample， the D- and Gbandsdisappear in the Raman spectra， primarily due to thedominated Ni and CoO particles which is consistent with TEMobservation in Fig. S6.

The pore structure of as-prepared Sb-C@RGO is investigatedby Brunauer-Emmet-Teller （BET） characterization. Fig. 3cshows the N2 adsorption/desorption isotherms of Sb-C@RGOwith a type H4 hysteresis at the high-pressure region， indicatingadsorption-desorption in narrow slitlike pores formed bystacking Sb-C@RGO sheets. The pore-size distribution curve inFig. 3d shows the pores of Sb-C@RGO are primarily mesoporesto macropores. The BET surface area and the pore volume valuesof Sb-C@RGO sample are evaluated to 54.65 m2?g?1 and 0.086cm3?g?1， respectively， which are lower than that of RGOsubstrate （Fig. S8）. On the contrary， Sb@RGO shows the lowBET surface area （18.30 m2?g?1） and the low adsorption volume（0.024 cm3?g?1）.

The XPS was further used to study the surfacecharacterization of as-prepared carbon. The full-scale XPSspectra reveal that both Sb-C@RGO and Sb@RGO samples aremainly composed by C， O， N， and Sb atoms. No Co and Nisignals were detected in Sb@RGO， which is probably due to thatformed Sb was coated on Ni and CoO particles after the galvanicreplacement reaction. The Sb 3d spectrum of Sb-C@RGOsample shows two peaks at 530.55 and 539.90 eV，corresponding to Sb 3d5/2 and Sb 3d3/2 of Sb2O3 20， indicating thepartial oxidation of Sb on the surface. The two Sb 3d XPS peaksfor Sb@RGO are negatively moved， which is mainly associatedto reduce oxidation degree of Sb in Sb@RGO. In view of that noSb2O3 signals are detected in the XRD and Raman spectra， it isspeculated that the oxidation is limited to the surface of the Sbparticles 20. TGA curve in Fig. S9 shows that the mass loadingof Sb in Sb-C@RGO sample is 77%.

The Na+ charge storage behavior of as-prepared samples wasinitially studied in a half-cell configuration vs. Na metal. Fig.S10 shows the CV curves of Sb-C@RGO at a sweep rate of 0.2mV?s?1 within a potential range of 0.01–3.00 V （vs. Na/Na+）.During the first discharging process， the large current response at the low potential around 0.89 V vs. Na/Na+， which is primallydue to the formation of solid electrolyte interface （SEI） 13，19. Inthe subsequent discharging process， two broad reduction peaks（around 0.90 and 0.32 V vs. Na/Na+） appear， stemming from themultistep alloying processes 19，20. These two broad reductionpeaks tend to be stable in the followed cycles. For the initialanodic scan， two peaks around 0.81 and 1.84 V vs. Na/Na+，corresponding to the multistep dealloying reactions from Na3Sbinto Sb 19，20， suggesting the good reversibility.

Fig. 4a displays the discharge/charge curves of the Sb-C@RGO in the initial ten cycles at a current density of 0.1 A?g?1.The first discharge curve with several plateaus exhibits the largeirreversible capacity， which is mainly due to the irreversiblereactions for SEI formation 19，20. In the followed chargingprocess， two plateaus around 0.75 and 1.75 V vs. Na/Na+ arefound and can regarded as the multistep dealloying reactionsfrom Na3Sb into Sb， which is consistent with CV observation.Only one prominent plateau around 1.0 V vs. Na/Na+ in thesecond discharging curve， corresponding to cathodic CV peak inFig. S10. In the subsequent charge/discharge processes， thecharge/discharge curves tend to overlap， suggesting the goodreversibility Sb-Na alloying/dealloying reactions on Sb-C@RGO. Fig. 4b displays the typical charge/discharge curvesranging from 0.1 to 10.0 A?g?1. These slope charge/dischargecurves under the high rates show the similar profile with thecharge/discharge curve at low rate of 0.1 A?g?1， indicating thehigh-rate capability. According to the charge/discharge curves atthe different rates， the specific capacities of Sb-C@RGO can beevaluated to 521.5， 433.5， 372.7， 332.6， 306.9， 263.5， 186.2，124.4 and 83.5 mAh?g?1， corresponding to the current densitiesof 0.1， 0.2， 0.5， 0.8， 1， 2， 5， 8 and 10 A?g?1， respectively. The values of specific capacity for Sb-C@RGO electrode are muchhigher than that of Sb@RGO electrode and are highlycomparable with other reported Sb anodes （Table S1， SupportingInformation）， which is primarily due to unique 2D nanostructurecomposed by ultra-small Sb nanoparticles and highly conductiveRGO， thus providing shorten Na+ diffusion path and large activesites for Na+ charge storage. To further unveil the fast kineticsof Na+ charge storage on Sb-C@RGO electrode， galvanostaticintermittent titration technique （GITT） was further carried out（Fig. S11）. The achieved GITT curves can be used to qualify theNa+ diffusion coefficient （Dk） through the Fick’s second law（Fig. 4d）. The Dk values for Sb-C@RGO fall in between 5.69 ×10?12 and 6.06 × 10?10 cm2?s?1， which is higher than that ofSb@RGO， suggesting the fast Na+ diffusion kinetics of Sb-C@RGO. Furthermore， Sb-C@RGO displays better cyclingstability than Sb@RGO （Figs. S12 and S13）.

To demonstrate the feasibility of Sb-C@RGO as the highperformanceelectrode for emerging energy-storage devices， ahybrid cell configuration （e.g.， SIC） was fabricated byemploying the Sb-C@RGO as the negative electrode （batterytype） and home-made activated carbon （PDPC） as the positiveelectrode （capacitive type） in a Na+ based organic electrolyte， asschematically illustrated in Fig. 5a. The lower potential andupper potential of SIC were set to 1.0 and 4.0 V， respectively，which is mainly because of avoiding the Na plating andoxidative decomposition of electrolytes. Fig. 5b displays theCVs of Sb-C@RGO//PDPC SIC under the different scan ratesfrom 5 to 80 mV?s?1. All these curves display the quasirectangularprofiles， which is mainly associated to thesynergistic effect of battery-type Sb-C@RGO electrode andcapacitive PDPC electrode. Even the scan rate is up to 80mV?s?1， the quasi-rectangular profile of CV curves is stillpreserved， suggesting the high-rate performance of as-fabricatedSIC. Fig. 5c displays the typical charge/discharge curves of Sb-C@RGO//PDPC SIC under the rates from 0.1 and 5 A?g?1. Allthese curves display the symmetric linear profile， furtherconfirming the excellent capacitive properties of Sb-C@RGO//PDPC SIC. From the discharge/charge curves （Fig.5d）， the specific capacities of Sb-C@RGO//PDPC SIC can bequalified to 56.5， 52.4， 47.0， 43.0， 40.7 and 33.9 mAh?g?1，corresponding to 0.1， 0.2， 0.5， 0.8， 1 and 2 A?g?1. Even thecurrent density increases to 5 A?g?1， further demonstrating thegood rate capability. Nyquist plot （achieved at 2.5 V with thefrequency range from 0.01 to 105 Hz） shown in Fig. 5e displaysa semicircle in the high frequency area and an approximatelyvertical curve in the low frequency area， suggesting a nearlycapacitive behavior of as-fabricated Sb-C@RGO//PDPC SIC.

Fig. 5f displays the Ragone plot （energy density vs. powerdensity） of as-prepared SIC. Our Sb-C@RGO//PDPC SICexhibits a high energy density of 140.75 Wh?kg?1 at a powerdensity of 250.84 W?kg?1. Even the power density is magnified～50 times to 12.43 kW?kg?1， this SIC still delivers a high energydensity of 55 Wh?kg?1. Therefore， within a shortcharge/discharge of ～3.2 min， Sb-C@RGO//PDPC SIC canstore/release quite a high energy density of 108.5 Wh?kg?1. Fig.5f further shows that the energy and power densities of Sb-C @RGO//PDPC SIC are highly comparable to many state-of-artreported SICs， including V2O5-CNTs//activated carbon （AC） 38，MoSe2/G//AC 39， TiO2-C//AC 40， N-Ti3C2Tx//AC 41， Hardcarbon//Graphene 42， Na2Ti3O7//AC 43， MoS2-C//C-HNT 44，（POM）@Mxene//AC 45， MWTOG//AC 46， AC//VS4-CNT 47，HC//AC 48， In6S7//AC 8， and other Sb anodes based SICs （TableS2）. In addition， Sb-C@ RGO//PDPC SIC shows the goodcycling stability with an acceptable capacity retention value of66.27% after 1000 cycles at a current density of 2 A?g?1. TheCoulombic efficiency is approximate 100% during the wholecycling process.

4 Conclusions

In summary， we have demonstrated that graphene could beused an ideal substrate to anchoring Sb nanoparticles by a facilepyrolysis process and galvanic replacement reaction with theassistance of PDA coating. The 2D layered structure of Sb-C@RGO composite increases the atomic interface contact withNa+ and provides shortened ion diffusion path， thus facilitatingcharge transfer. Half-cell test shows that Sb-C@RGO delivers ahigh reversible specific capacity of 521.5 mAh?g?1 at a currentdensity of 0.1 A?g?1 and a high rate capability of 83.5 mAh?g?1at 10 A?g?1. SICs were fabricated by employing Sb-C@RGOcomposite as the negative electrode and home-made PDPC asthe positive electrode， which delivers an energy density of140.75 Wh?kg?1 at 250.84 W?kg?1 and remains 55 Wh?kg?1 evenat a high power density of 12.43 kW?kg?1. These findings mayprovide a way for designing 2D layered composite with largeactive sites and shorten ion diffusion path toward highperformancesodium-ion based energy storage devices includingcapacitors and batteries.

Author Contributions： Conceptualization， Mi， C. L.， Qin，Y. Y.， Shi， Y. C. and Wang， R. T.; Methodology， Huang， X. L.;Software， Mi， C. L.; Validation， Mi， C. L.， Qin， Y. Y. and Huang，X. L.; Formal Analysis， Qin， Y. Y.; Investigation， Luo， Y. J.;Resources， Huang， X. L.; Data Curation， Mi， C. L.; Writing –Original Draft Preparation， Mi， C. L. and Wang， R. T.; Writing –Review amp; Editing， Wang， R. T. and Shi， Y. C.; Visualization，Zhang， Z. W.; Supervision， Wang， C. X.; Project Administration， Yin， L. W and Wang. R. T.

Supporting Information： available free of charge via theinternet at http：//www.whxb.pku.edu.cn.

References

（1） Vaalma， C.; Buchholz， D.; Weil， M.; Passerini， S. Nat. Rev. Mater.2018， 3， 18013. doi： 10.1038/natrevmats.2018.13

（2） Chayambuka， K.; Mulder， G.; Danilov， D. L.; Notten， P. H. L. Adv.Energy Mater. 2020， 10， 2001310. doi： 10.1002/aenm.202001310

（3） Zhang， Z. H.; Gu， Z. H.; Zhang， C. G.; Li， J. B.; Wang， C. Y.Batteries Supercaps 2021， 4， 1680. doi： 10.1002/batt.202100042

（4） Cai， P.; Zou， K. Y.; Deng， X. L.; Wang， B. W.; Zheng， M.; Li， L. H.;Hou， H. S.; Zou， G. Q.; Ji， X. B. Adv. Energy Mater. 2021， 11，2003804. doi： 10.1002/aenm.202003804

（5） Wang， H. W.; Zhu， C. R.; Chao， D. L.; Yan， Q. Y.; Fan， H. J. Adv.Mater. 2017， 29， 1702093. doi： 10.1002/adma.201702093

（6） Chang， X. Q.; Huang， T. Y.; Yu， J. Y.; Li， J. B.; Wang， J.; Wei， Q. L.Batteries Supercaps 2021， 4， 1567. doi： 10.1002/batt.202100043

（7） Ding， J.; Hu， W. B.; Paek， E.; Mitlin， D. Chem. Rev. 2018， 118， 6457.doi： 10.1021/acs.chemrev.8b00116

（8） Zhu， C. Y.; Yu， W. Q.; Zhang， S. X.; Chen， J. C.; Liu， Q. Y.; Li， Q. Y.;Wang， S. J.; Hua， M. H.; Lin， X. H.; Yin， L. W.; et al. Adv. Mater.2023， 35， 2211611. doi： 10.1002/adma.202211611

（9） Yu， W. Q.; Zhu， C. Y.; Wang， R. T.; Chen， J. C.; Liu， Q. Y.; Zhang， S.X.; Zhang， S. B.; Sun， J. F.; Yin， L. W. Energy Environ. Mater. 2023，6， 12337. doi： 10.1002/eem2.12337

（10） Zhang， H.; Hasa， I.; Passerini， S. Adv. Energy Mater. 2018， 8，1702582. doi： 10.1002/aenm.201702582

（11） Lao， M. M.; Zhang， Y.; Luo， W. B.; Yan， Q. Y.; Sun， W. P.; Dou， S. X.Adv. Mater. 2017， 29， 1700622. doi： 10.1002/adma.201700622

（12） Hou， H. S.; Qiu， X. Q.; Wei， W. F.; Zhang， Y.; Ji， X. B. Adv. EnergyMater. 2017， 7， 1602898. doi： 10.1002/aenm.201602898

（13） Yu， W. Q.; Zhu， C. Y.; Wang， R. T.; Chen， J. C.; Liu， Q. Y.; Zhang， S.X.; Gao， Z. J.; Wang， C. X.; Zhang， Z. W.; Yin， L. W. Rare Metals2022， 41， 3360. doi： 10.1007/s12598-022-02015-z

（14） Yin， J.; Qi， L.; Wang， H. Y. ACS Appl. Mater. Interfaces 2012， 4，2762. doi： 10.1021/am300385r

（15） Yuan， J.; Qiu， M.; Hu， X.; Liu， Y. J.; Zhong， G. B.; Zhan， H. B.; Wen，Z. H. ACS Nano 2022， 16， 14807. doi： 10.1021/ acsnano.2c05662

（16） Ma， Y.; Zhang， L. Y.; Yan， Z. X.; Cheng， B.; Yu， J. G.; Liu， T. Adv.Energy Mater. 2022， 12， 2103820. doi： 10.1002/aenm. 202103820

（17） Liu， C.; Zhang， M. X.; Zhang， X.; Wan， B.; Li， X. N.; Gou， H. Y.;Wang， Y. X. Yin， F. X.; Wang， G. K. Small 2020， 16， 2004457.doi： 10.1002/smll.202004457

（18） Zhao， R. Z.; Di， H. X.; Wang， C. X.; Hui， X. B.; Zhao， D. Y.; Wang，R. T.; Zhang， L. Y.; Yin， L. W. ACS Nano 2020， 14， 13938.doi： 10.1021/acsnano.0c06360.

（19） Li， Q. H.; Zhang， W.; Peng， J.; Zhang， W.; Liang， Z. X.; Wu， J. W.;Feng， J. J.; Li， H. X.; Huang， S. M. ACS Nano 2021， 15， 15104.doi： 10.1021/acsnano.1c05458

（20） Yang， K. X.; Tang， J. F.; Liu， Y.; Kong， M.; Zhou， B.; Shang， Y. C.;Zhang， W. H. ACS Nano 2020， 14， 5728.doi： 10.1021/acsnano.0c00366

（21） Liu， Z. M.; Yu， X. Y.; Lou， X. W.; Paik， U. Energy Environ. Sci. 2016，9， 2314. doi：10.1039/c6EE01501H

（22） He， M.; Kravchyk， K.; Walter， M.; Kovalenko， M. V. Nano Lett.2014， 14， 1255. doi： 10.1021/nl404165c

（23） Liu， J.; Yu， L. T.; Wu， C.; Wen， Y. R.; Yin， K. B.; Chiang， F. K.; Hu，R. Z.; Liu， J. W.; Sun， L. T.; Gu， L.; et al. Nano Lett. 2017， 17， 2034.doi： 10.1021/acs. nanolett.7b00083

（24） Liu， Y.; Zhou， B.; Liu， S.; Ma， Q. S.; Zhang， W. H. ACS Nano 2019，13， 5885. doi： 10.1021/acsnano. 9b01660

（25） Hou， Z. G.; Zhang， X. Q.; Chen， J. W.; Qian， Y. T.; Chen， L. F.; Lee，P. S. Adv. Energy Mater. 2022， 12， 210453.doi： 10.1002/aenm.202104053

（26） Bi， X. Y.; Li， M. C.; Zhou， G. Q.; Liu， C. Z.; Huang， R. Z.; Shi， Y.;Xu， B. B.; Guo， Z. H.; Fan， W.; Algadi， H.; et al. Nano Res. 2023， 16，7696. doi： 10.1007/s12274-023-5586-1

（27） Duan， J.; Zhang， W.; Wu， C.; Fan， Q. J.; Zhang， W. X.; Hu， X. L.;Huang， Y. H. Nano Energy 2015， 16， 479.doi： 10.1016/j.nanoen.2015.07.021

（28） Xiao， B.; Sun， Z.; Zhang， H.; Wu， Y.; Li， J.; Cui， J.; Han， J.; Li， M.;Zheng， H.; Chen， J.; et al. Energy Environ. Sci. 2023， 16， 2153.doi： 10.1039/D2EE03970B

（29） Li， H. M.; Wang， K. L.; Zhou， M.; Li， W.; Tao， H. W.; Wang， R. X.;Cheng， S. J.; Jiang， K. ACS Nano 2019， 13， 9533.doi： 10.1021/acsnano.9b04520

（30） Chen， B. C.; Qin， H. Y.; Li， K.; Zhang， B.; Liu， E. Z.; Zhao， N. Q.;Shi， C. S.; He， C. N. Nano Energy 2019， 66， 104133.doi： 10.1016/j.nanoen.2019.104133

（31） Guo， X.; Gao， H.; Wang， S. J.; Yang， G.; Zhang， X. Y.; Zhang， J. Q.;Liu， H.; Wang， G. X. Nano Lett. 2022， 22， 1225.doi： 10.1021/acs.nanolett.1c04389

（32） Dong， W. X.; Qu， Y. F.; Liu， X.; Chen， L. F. Flatchem 2023， 37，100467. doi： 10.1016/j.flatc.2022.100467

（33） Yao， J. J.; Li， F. Z.; Zhou， R. Y.; Guo， C. C.; Liu， X. R.; Zhu， Y. R.;Chin. Chem. Lett. 2023， 108354. doi： 10.1016/j.cclet.2023.108354

（34） Bo， Z.; Kong， J.; Yang， H. C.; Zheng， Z. W.; Chen， P. P.; Yan， J. H.;Cen， K. F. Acta Phys. -Chim Sin. 2022， 38， 2005054. [薄拯， 孔競，楊化超， 鄭周威， 陳鵬鵬， 嚴(yán)建華， 岑可法. 物理化學(xué)學(xué)報， 2022，38， 2005054.] doi： 10.3866/PKU.WHXB202005054

（35） Shao， M. J.; Li， C. X.; Li， T.; Yu， W. Q.; Wang， R. T.; Zhang， J.; Yin，L. W. Adv. Funct. Mater. 2020， 30， 2006561.doi： 10.1002/adfm.202006561

（36） Tang， T.; Jiang， W. J.; Liu， X. Z.; Deng， J.; Niu， S.; Wang， B.; Jin， S.F.; Zhang， Q.; Gu， L.; Hu， J. S.; et al. J. Am. Chem. Soc. 2020， 142，7116. doi： 10.1021/jacs.0c01349

（37） Pu， B.; Liu， Y.; Bai， J.; Chu， X.; Zhou， X. F.; Qing， Y.; Wang， Y. B.;Zhang， M. Z.; Ma， Q. S.; Xu， Z.; et al. ACS Nano 2022， 16， 18746.doi： 10.1021/acsnano.2c07472

（38） Chen， Z.; Augustyn， V.; Jia， X. L.; Xiao， Q. F.; Dunn， B.; Lu， Y. F.ACS Nano 2012， 6， 4319. doi： 10.1021/nn300920e

（39） Kirubasankar， B.; Vijayan， S.; Angaiah， S. Sustain. Energy Fuels2019， 3， 467. doi： 10.1039/C8SE00446C

（40） Li， H， X.; Lang， S. L.; Chen， J. T.; Wang， K. J.; Liu， L. Y.; Zhang， T.Y.; Liu， W. S.; Yan， X. B. Adv. Funct. Mater. 2018， 28， 1800757.doi： 10.1002/adfm.201800757

（41） Fan， Z. D.; Wei， C. H.; Yu， L. H.; Xia， Z.; Cai， J. S.; Tian， Z. N.; Zou，G. F.; Dou， S. X.; Sun， J. Y. ACS Nano 2020， 14， 867.doi： 10.1021/acsnano.9b08030

（42） Wang， S. J.; Wang， R. T.; Zhang， Y. B.; Jin， D. D.; Zhang， L. J. PowerSources 2018， 379， 33. doi： 10.1016/j.jpowsour.2018.01.019

（43） Dong， S. Y.; Shen， L. F.; Li， H. S.; Pang， G.; Dou， H.; Zhang， X.G.Adv. Funct. Mater. 2016， 26， 3703. doi： 10.1002/adfm.201600264

（44） Gao， J. Y.; Li， Y. P.; Liu， Y.; Jiao， S. H.; Li， J.; Wang， G. R.; Zeng， S.Y.; Zhang， G. Q. J. Mater. Chem. A 2019， 7， 10028.doi： 10.1039/C9TA05666A

（45） Chao， H. X.; Qin， H. Q.; Zhang， M. D.; Huang， Y. C.; Gao， L. F.; Gu，H. L.; Wang， K.; Teng， X. L.; Cheng， J. K.; Lu， Y. K.; et al. Adv.Funct. Mater. 2021， 31， 2007636. doi： 10.1002/adfm.20200636

（46） Le， Z. Y.; Liu， F.; Nie， P.; Li， X. R.; Liu， X. Y.; Bian， Z. F.; Chen， G.;Wu， H. B.; Lu， Y. F. ACS Nano 2017， 11， 2952.doi： 10.1021/acsnano.6b08332

（47） Song， Z. R.; Zhang， G. Y.; Deng， X. L.; Tian， Y.; Xiao， X. H.; Deng，W. T.; Hou， H. S.; Zou， G. Q.; Ji， X. B. Adv. Funct. Mater. 2022， 32，2205453. doi： 10.1002/ adfm.202205453

（48） Liu， Q. Y.; Chen， J. C.; Du， D. N.; Zhang， S. X.; Zhu， C. Y.; Zhang， Z.W.; Wang， C. X.; Yin， L. W.; Wang， R. T. J. Mater. Chem. A 2023，doi： 10.1039/D3TA01098H

國家自然科學(xué)基金（52272224， 5190218）， 山東省科技型中小企業(yè)創(chuàng)新能力提升工程（2021TSGC1149）和山東省高等學(xué)校青年創(chuàng)新團隊發(fā)展計劃（10000082295015）資助項目