Homologous Hierarchical Porous Hollow Carbon Spheres Anode and

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Homologous Hierarchical Porous Hollow Carbon Spheres Anode and Bowls Cathode Enabling High-Energy Sodium-Ion Hybrid Capacitors Daping Qiu, Ang Gao, Zhenyu Xie, Lun Zheng, Cuihua Kang, Yan Li, Nannan Guo, Min Li, Feng Wang, and Ru Yang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b16442 • Publication Date (Web): 04 Dec 2018 Downloaded from http://pubs.acs.org on December 5, 2018

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Homologous Hierarchical Porous Hollow Carbon Spheres Anode and Bowls Cathode Enabling HighEnergy Sodium-Ion Hybrid Capacitors Daping Qiu †, Ang Gao†, Zhenyu Xie†, Lun Zheng†, Cuihua Kang†, Yan Li†, Nannan Guo †,§, Min Li*,†, Feng Wang*,†,‡ and Ru Yang*,† †State

Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of

Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, China. ‡Beijing

Advanced Innovation Center for Soft Matter Science and Engineering, Beijing

University of Chemical Technology, Beijing 100029, China. §Key

Laboratory of Energy Materials Chemistry, Ministry of Education, Key Laboratory of

Advanced Functional Materials, Autonomous Region, Institute of Applied Chemistry, Xinjiang University, Urumqi 830046, Xinjiang, China.

ABSTRACT: It is a highly expected avenue to construct dual-carbon sodium-ion hybrid capacitors (SIHCs) using hierarchical porous carbon with interconnected pores, high accessible surface area and disordered carbon frameworks for ameliorating the sluggish kinetics of SIHCs. In this work, a novel dual-carbon SIHCs system with homologous enhanced kinetics hierarchical porous hollow carbon spheres (HPCS) and hierarchical porous hollow carbon bowls (HPCB) as


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the anode and cathode is constructed for the first time. In a Na half-cell configuration, the HPCS anode synthesized through a facile one-pot in-situ template route demonstrates a superior reversible capacity as well as outstanding rate capability and cycleability, and the HPCB cathode fabricated by chemical activation of HPCS exhibits excellent capacitive behaviors. Thanks to superiorities of properties and structures of the anode and cathode, the constructed novel dualcarbon SIHCs present an exceptionally high energy/power density (128.5 Wh kg−1 and 11.9 kW kg−1), along with long cycling lifespan with retained morphology. This study on kinetics enhanced dual-carbon SIHCs opens a new avenue for optimizing the microstructure of hierarchical porous carbon and constructing new type high-performance SIHCs systems.

KEYWORDS: Homologous hierarchical porous carbon, hollow carbon spheres, hollow carbon bowls, dual-carbon, fast kinetics, sodium-ion hybrid capacitors

INTRODUCTION Metal-ion batteries (MIBs) and supercapacitors (SCs) are recognized as two the most promising energy storage systems for renewable energy.1−4 However, MIBs hamper from low power density and short cycling life due to the sluggish kinetics behavior during charging/discharging process, by contrast, SCs suffer from unsatisfactory energy density owing to low potential window.5−7 Metal-ion hybrid capacitors (MIHCs), a burgeoning energy storage device that bridge the complementary advantages of MIBs and SCs by delivering acceptable energy at high power without sacrificing the cycleability, is the most promising one to play this role.8,9 Further, considering the restriction of precursor supply to Lithium-ion hybrid capacitors, increasing research efforts have shifted to explore sodium-ion hybrid capacitors (SIHCs) with higher precursor abundance in recent years.10−12


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A typical SIHC is composed of a battery-type anode, a capacitor-type cathode, and the corresponding organic electrolyte.3,4 In the charging process, cations migrate and insert into the anode, meanwhile anions in electrolyte migrate and adsorb to the cathode. In the discharging process, cations extract from the anode, and anions desorb from the cathode.9,12,13 So far, most reported SIHCs are based on the coupling of battery-type anode with carbon-based cathode, such as NaTi2(PO4)3//graphene,14 E-MoS2@carbon fibers//AC,15 Na2Ti2O5−x//rGO/AC film,16 TiO2−x/CNT//AC/CNT,17 Gr-Nb2O5//AC,18 and much more. However, most of these reported SIHCs still fall far short of actual application requirements due to the slow kinetics of the whole systems. Designing and preparing new SIHCs with the right combination of battery-type and capacitor-type electrodes is extremely urgent. In the view of structure, the key to constructing a fast kinetics SIHCs system is the high performance cathode and anode with similar microstructure.19−21 To this end, constructing a dual-carbon SIHCs both anode and cathode composed of carbon materials, is a feasible avenue to ameliorate kinetics defects. Considering the reality, microstructurally designed carbons are probably the most economically and technically feasible candidates for SIHCs applications.3 For carbon-based anode materials, it has unparalleled superiorities over other categories of materials in terms of kinetics and long-term cycleability, the critical point to ameliorate the performance of carbonbased anode is to enhance its reversible capacity. Considering the structure, the enhancement of reversible capacity mainly depends on three aspects: intrinsic carbon framework, surface pore distribution and heteroatoms (N, O etc.). Namely, disordered nongraphitized carbon framework possesses a higher battery capacity, optimized surface pore size distribution contributes to a higher capacitive capacity, and a certain content of heteroatoms induce an extra Faradic capacity.4,19−21 In general, the overly disordered carbon framework is not conducive to ion


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conduction. Hence, adjusting the surface pore size distribution and heteroatoms content is a more reasonable idea to improve the reversible capacity of carbon-based anodes.3,22 On this account, carbon-based materials with tunable microstructure, such as carbon nanosheets,17 ordered mesoporous carbon,23 hollow carbon spheres,24 graphene,25 etc. are expected to be promising SIHCs anodes. Among all the candidates, hierarchical porous hollow carbon spheres (HPCS) are highly fascinating for their unique microporous/mesoporous hierarchical shell−macropores cavity structures.24,26,27 To the best of our knowledge, almost all related studies focused only on enhancing the performance of battery-type anode and neglected the role of capacitor-type cathode. However, based on the formula C = 1/Canode + 1/Ccathode, a capacitor-type cathode with optimized performance is equally important for constructing promising SHICs.21,22 In the view of supercapacitor electrode materials, ion accessible surface area plays a key parameter to evaluate the capacitive behavior of carbon electrodes, to this end, various porous carbons are the most frequently selected material.28−30 However, for the cathodes without optimized pore structure, not all pores are ion accessible at high current density due to the irrational pore structure, despite the high porosity and large surface area.23,31 The key point to ameliorating the cathode performance of SIHCs is to improve the porosity utilization at high current density. So far, hierarchical porous carbon with optimized pore structure is the most recognized choice for almost all carbon materials, and it is certainly a suitable SIHCs cathode material. Herein, with the aim of constructing ideal dual-carbon SIHCs, a facile one-pot in-situ template route has been developed to synthesize monodispersed HPCS and its hierarchical porous hollow bowls (HPCB) counterparts. The as-synthesized HPCS have an amorphous carbon frameworks, interconnected hierarchical porous structure, and a certain degree of N content (2.24


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at %). When evaluated as anode for SIHCs, the HPCS anode exhibits a high reversible capacity, outstanding rate capability and long-life capability. HPCB with optimized hierarchical pore structure and denser packing density are fabricated by KOH activation of HPCS. Benefiting from the optimized hierarchical porous structure, the symmetrical supercapacitors assembled based on HPCB electrodes exhibit excellent capacitive behaviors. Furthermore, we have constructed a new dual-carbon SIHCs system that merges the merits of HPCS and HPCB. This new dualcarbon SIHCs present an exceptionally high energy and power density (128.5 Wh kg−1 and 11.9 kW kg−1) as well as long cycling lifespan. RESULTS AND DISCUSSION As illustrated in Figure 1a, in a typical one-pot in-situ template route of HPCS, in situ generated silica spheres and 3-AP/formaldehyde polycondensates (APF) are selected as templates and carbon precursor, respectively. Notably, the formation of SiO2 core and primary particle is controlled by the hydrolysis and condensation rate of tetrapropyl orthosilicate (TPOS).32 After a long period of polymerization, SiO2@APF colloidal nanospheres with uniform size and adherence appear. Then the subsequent carbonization and removal of templates, HPCS are successfully prepared (Figure S1). The SEM and TEM images reveal that HPCS-800 has a welldefined hollow spherical morphology with rough surface (Figure 1b, f and Figure S2a, e). Meanwhile, the thickness of the shell is about 27 nm in the light of HRTEM image (Figure S5a). In addition, SEM images of HPCS at different carbonization temperatures show that 700-800 °C is the suitable temperature to maintain ideal spherical morphology (Figure S3). Finally, HPCB with a variety of morphologies are successfully prepared by adjusting the KOH dosage. The SEM and TEM images of HPCB show a clearer bowl-like morphology with the increase of the KOH dosage (Figure 1c-e and Figure S2). Notably, HRTEM images suggest that higher the


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Figure 1. (a) Schematic illustration of the synthesis of HPCS and HPCB. SEM images of (b) HPCS, (c) HPCB-1, (d) HPCB-2, (e) HPCB-3. TEM images of (f) HPCS-800, (g) HPCB-1, (h) HPCB-2, (i) HPCB-3. (j) The morphological evolution process of HPCS during KOH activation.

KOH dosages correspond to thinner the HPCB shells (Figure S5). As shown in the diagram (Figure 1j), the morphological evolution from HPCS-800 to HPCB is a process of spherical shell depression, and the degree of depression is positively correlated with the KOH dosage. Low KOH dosage could etch the shell to enhance the porosity of the spherical shell (HPCB-1), and


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under high KOH dosage, the seriously etched shell will collapse inward depression to form bowl-like morphology for mechanical reasons.33,34 It is worth noting that the previously reported HPCB synthesis process usually involves the regulation of multiple raw material dosages, with complex and uncertain processes, which is far less than the application value of the KOH activation.35 The porosities of HPCS-800 and HPCB are further investigated by the N2 adsorptiondesorption studies (Figure 2a-c and Table S1). HPCS-800 (Figure 2a) exhibits a typical type IV isotherm with a clear H3 hysteresis loop, and the corresponding pore size distribution (PSD) curve displays a minisize mesopores dominated hierarchical pore structure.36 The specific surface area (SSA) is as high as 1369 m2 g-1, and 77% of total pore volume comes from minisize mesopores (Table S1). Distinguished from HPCS, the type IV isotherms with a clear H4 hysteresis loop are obtained after the KOH activation (Figure 2b), and the corresponding PSD curves show that micropores dominate the hierarchical pore structure. With the increasing of the KOH dosage, the SSA of HPCB-1, HPCB-2 and HPCB-3 increase to 1774, 2189, and 2126 m2 g1,

and the micropores pore volumes correspondingly increase from 0.18 to 0.365, 0.492 and 0.51

m3 g−1 (Table S1) , respectively. Notably, owing to the collapse of partial mesopores caused by excessive activation at high KOH dosage, the specific surface area of HPCB-3 is slightly lower than HPCB-2. For carbon-based anode materials, the mesopores dominated hierarchical pore structure not only provides ion transport channels, but also contributes to capacitive capacity.24,26 For capacitor-type cathode materials, high active micropores (about 0.7-2.0nm) content is vital for the capacitive behavior of the cathode.37,38 In the view of PSD, HPCS meets the requirements of carbon-based anode and HPCB is a promising capacitor-type cathode. Further, , both HPCS and HPCB possess the microporous/mesoporous shell-macroporous cavity type interconnect


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channel structure (Figure S5), such ion-permeable open channels play an important role in promoting ion diffusion in electrochemical process.39

Figure 2. (a) N2 adsorption-desorption isotherms curves of (a) HPCS-800, (b) HPCB; (c) DFT pore size distribution, (d) XRD patterns (insert is the interlayer spacing of HPCS calculated according to HRTEM image), (e) Raman spectra, (f) XPS survey spectra of HPCS-800 and HPCB.

The XRD patterns of HPCS-800 and HPCB are displayed in Figure 2d, in which all the samples display two broad peaks centered at approximately 23.1° and 43°, corresponding to the (002) and (001) crystallographic planes of the graphitic structure, respectively.40,41 Further analysis of the XRD patterns indicates that HPCS-800 has relatively strong (002) and (001) peaks, and the interlayer spacing is up to 4.17 Å (inset of Figure 2d, calculated according to Figure S5e), which means that HPCS-800 is wide-interlayer carbon with a certain graphitization degree. On the contrary, the intensity of corresponding diffraction peaks is greatly reduced after the KOH activation, which is attributed to the reduction in graphitization degree caused by the etching effect of KOH. This result is validated by Raman spectra, the Raman spectra of HPCS-


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800 and HPCB (Figure 2e) show two peaks at 1344 cm−1 (D-band, A1g vibration mode present in disordered sp3 C atoms) and 1590 cm−1 (G-band, E2g graphitic mode of pairs of sp2 C atoms), respectively.42,43 The intensity ratio (ID/IG) between the D-band and the G-band is a vital indicator of the ordering degree of the carbon-based materials. Lower ID/IG values of HPCS than those of KOH activated samples confirm that KOH etching results in a decrease of graphitization degree, or an increase of defects. In addition, the HRTEM images and corresponding SAED patterns of all samples from a structural perspective show that the KOH activation results in the disordered carbon frameworks (Figure S5 e-l). Moreover, the nearly identical radius of the diffraction ring indicates that all samples possess the same interlayer spacing. It is worth noting that a wider interlayer spacing and a certain degree of graphitization play positive parts in enhancing the reversible capacity of battery-type anode.19,20 Further structural information of the HPCS-800 and HPCB are obtained by FTIR and XPS analysis. As shown in FTIR spectra (Figure S4a), there is no significant difference in the types of surface groups between HPCS-800 and HPCB. In addition, the intensity of the -OH (~3434 cm−1) and C-O (1250-980 cm−1) absorption peaks of HPCB are significantly stronger than HPCS, which may be related to the introduction of more oxygen-containing groups after the KOH activation. XPS test is performed to analyze the surface characteristics of HPCS-800 and HPCB (Figure 2f, S4 , Table S2). As shown in Figure. 2f, the survey spectrum exhibits the existence of C, O, and N. The relative peak intensity of the O increases with an increasing KOH dosage, indicating an increase in the corresponding content percentage. In contrast, the content percentage of N decreases with an increasing KOH dosage. Detailed elemental analysis data are shown in Table S2. HPCS-800 possesses the highest N content (about 2.24%), while HPCB-3 exhibits the highest O content (about 5.38%). The deconvolution XPS profiles of C 1s and O 1s


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Figure 3. Electrochemical performance of HPCS-800 anode. (a) CV curves of the first three cycles at the scan rate of 0.5 mV s−1. (b) GCD profiles of the first three cycles at the current density of 0.1 A g−1. (c) CV curves at different scan rates. (d) b-value determination of the cathodic and anodic peak currents, R2 values are the fitting variance of b-values. (e) Rate capability test. (f) Cycling performance at the current density of 0.1 A g−1. (g) Ultralong cycling performance at the current density of 5 A g−1. (h) Capacitive (green region) and diffusioncontrolled (white region) contribution to charge storage of HPCS-800 at 5 mV s−1. (i) Normalized contribution ratio of capacitive and diffusion-controlled capacities at different scan rates.

are displayed for the quantitative analysis of surface elements (Figure S4b, c). The C 1s spectrum contains four component peaks centered at 284.7, 285.3, 288.0, and 289.9 eV, representing CC/C=C, C-O/C-N, C=O, and O-C=O, respectively.35 Consistent with C1s, the O 1s spectrum


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contains three peaks at 531.6, 532.7, and 534.0 eV, which represent C=O quinone-type (O-I), COH phenol-type groups (O-II), and the oxygen of carboxylic groups or water (O-III), respectively, which have a positive effect on the electrochemical performance of the carbon materials.

31,44

Notably, the only peak of fitted N 1s spectrum (Figure S4d) at 400.1 eV is

assigned to pyrrolic N (N-5), which can enhance the reversible capacity of carbon anode via reversible binding with Na+. XPS results show that both HPCS-800 and HPCB have considerable content of heteroatoms (N and O), which are expected to enhance the capacitive behaviors for both anode and cathode.19,26 The electrochemical properties of HPCS as anode for SIHCs are evaluated using cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD). The initial three CV curves of HPCS-800 measured at 0.5 mV s-1 are displayed in Figure 3a. The curve of the first cycle shows a different shape from the other cycles, and broad reduction peaks within the region of 0.3-0.6 V, suggesting the decomposition of electrolyte and development of SEI layer. Meanwhile almost overlapping curves in subsequent cycles indicates the stable reversibility of the HPCS-800.45,46 Figure 3b presents the GCD profiles of HPCS-800 for the initial three cycles at 0.1 A g−1. During the initial cycle, discharge and charge capacities are up to 2216 and 728 mA h g-1, respectively, resulting in a low initial coulombic efficiency of 32.8%, due to the formation of SEI layer or the decomposition of electrolyte.46,47 The rate performance of the HPCS-800 anode at the current densities of 0.2−20 A g-1 is displayed in Figure 3e. The reversible capacity changed from 347.8 to 133.3 mA h g−1 when the current density increases from 0.2 to 20 A g−1. Further, when the current density decreases back to 1 A g-1, the reversible capacity can still be turned back to 230 mA h g-1, suggesting the superior rate capability and reversibility of HPCS-800 anode, which can be attributed to its structural stability and hierarchical porous structure. In addition, as shown in


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Figure S6, HPCS-800 exhibits a much higher capacity than HPCS-700, HPCS-900, and HPCS1000. The cycling performances of the HPCS-800 anode are further examined at 0.1 and 5 A g-1, respectively. As shown in Figures 3f, HPCS-800 anode delivers a stable reversible capacity of 490 mA h g−1 with nearly 100% coulombic efficiency after 10 cycles at 0.1 A g−1. Further test with over 5000 continuous cycles at a high current density of 5 A g−1 also displays a stable reversible capacity of 190 mA h g−1, and remain negligible degradation from the 80 to 5000 cycles (Figures 3g). What's more, HPCS-800 can still maintain an integrated hollow spherical morphology without obvious splitting after 5000 cycles (Figure S7). The superior long cycling lifespan of the HPCS-800 anode can be mainly ascribed to the formation of a sturdy SEI layer in the initial several cycles. These results indicat that HPCS-800 with high reversible capacity, superior rate capability and long cycling lifespan can act as a potential anode material for the construction of SIHCs. Such excellent electrochemical performances are superior to many previously reported carbonaceous anode materials for SIHCs or SIBs (Table S3). According to the CV curves at different scan rates (Figure 3c), the sodium storage kinetics of HPCS-800 anode is evaluated using the following equation:48 i = avb

(1)

where the peak current(i) depends on the scan rate(v), and a b value of 0.5 indicates that the current is diffusion-controlled while b value of 1 reveals capacitive behavior (surfacecontrolled).48,49 Figure 3d shows the log(i) − log(v) plots of HPCS-800 anode and the R2 of both anode and cathode plots are close to 1. The b-value of anode and cathode are 0.8666 and 0.7042, respectively, which demonstrate combined contributions from capacitive processes and intercalation reactions.


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To further evaluate the contribution from the capacitive processes and intercalation reactions, an analysis method as described in Eq. (2) was proposed.50,51 i(V) = k1v + k2v1/2

(2)

where i(V) is the current response at a chosen voltage, by determining both k1 and k2, the percentage of current contributed by capacitive processes and intercalation reactions can be calculated as a function of potential. Figure 3h exhibits the CV curve of HPCS-800 at 5 mV s−1 as well as the capacitive processes contribution (green region) calculated based on the preceding analysis method, the capacitive-controlled capacity accounting for ∼59.5%. As expected, the contribution from the capacitive process increases from ~42.2% to 49.1, 59.5, 66.2 and 75.3% as the scan rate rises from 1 to 2, 5, 10 and 20 mV s-1, respectively (Figure 3i). These results imply that the capacitive behavior induced by hierarchical porous structure and heteroatoms plays a vital role in promoting the kinetics of HPCS-800 anode. Here HPCB is used as capacitor-type cathode for SIHCs, which is prepared by KOH activation of HPCS. To evaluate the capacitive charge storage properties of HPCB that prepared by different KOH dosages, symmetric supercapacitor devices are constructed using neat EMIM BF4 (1-ethyl-3-methylimidazolium tetrafluoroborate). Figure S8a, b show the CV and GCD curves of HPCB at 50 mV s-1 and 1 A g-1, suggesting all the HPCB based symmetric supercapacitors can operate stably at 3.0 V. HPCS-3 exhibits the largest current response in CV curves and longest discharge time in GCD curves, respectively. Hence, HPCB-3 demonstrates the highest specific capacitances at all current densities (Figure. S8c). The highest specific capacitance can reach up to 189.3 F g−1 at 1 A g−1, and retains a high value of 150.3 F g−1 even at 30 A g−1 (79.5% retention). Note that using carbon materials with pores greater than 0.7 nm


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allows the maximum double-layer capacitance in an organic electrolyte, consistently, HPCB-3 contains the most such micropores among all the samples (Table S1). 36,37

Figure 4. Electrochemical performances of HPCB-3 based symmetric supercapacitor in neat EMIM BF4 electrolyte. (a) CV curves at different scan rates. (b) GCD curves at different current densities. (c) Ragone plots in comparison with other literature works (inset is the digital photograph of LEDs powered by assembled symmetric supercapacitor). (d) Cycling stability at 10 A g−1. (e) Nyquist plots before and after 5000 cycles.

Figure 4 exhibit the electrochemical properties of the as-assembled HPCB-3 based symmetric supercapacitor. CV curves of HPCB-3 based supercapacitor display regular rectangular shapes even at 500 mV s−1 (Figure 4a), and GCD curves (Figure 4b) exhibit perfect isosceles triangle shapes even at 30 A g−1. Furthermore, the capacitance retention is 94.4% of the initial value after 5000 cycles at 10 A g-1 (Figure 4d). Figure 4e shows the Nyquists plots of HPCB-3 supercapacitor before and after 5000 cycles. Both Nyquist plots contain a semicircle in high frequency region and a straight line in low frequency regions. More specifically, their high


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frequency intercepts and semicircle are almost overlapped, suggesting nearly equal bulk solution resistance (Rs) and interfacial resistance of charge transfer (Rct), but the slop of their straight lines in low frequency are distinctly different, the slop of after 5000 cycles is smaller than that of before cycled, indicating that a higher diffusion resistance is experienced after 5000 cycles.52 The EIS analysis results indicate that EMIM BF4 will not decompose under the voltage of 3V, and the capacity loss of 5000 cycles comes from slight structural failure. Figure 4c further gives the Ragone plot of the HPCB-3 based supercapacitor, it can achieve energy densities of 58.6 and 31.9 Wh kg−1 at power densities of 1493 and 37.1 kW kg−1, respectively, superior to most of those previous reported carbon-based supercapacitors in ionic liquid electrolyte or organic electrolyte.21,53−62 More importantly, HPCB-3 based

symmetric supercapacitor can light a

“carbon pattern” consisting of 93 blue light-emitting diodes (operating voltage 3 V, 20 mA), as shown in inset of Figure 4c. To further investigate the electrochemical performances of HPCBbased cathode, a half-cell configuration with sodium wafer as the counter electrode is utilized. Consistent with the results of symmetric supercapacitors, HPCB-3 cathode demonstrates a much higher specific capacity than other samples (Figure S9a). Figure S9b,c shows the CV and GCD profiles of HPCB-3 cathode over 2.0−4.0 V, both of which indicate an acceptable capacitive behavior. HPCB-3 cathode delivers high specific capacitance of 198.7 F g−1 at 0.1 A g−1 and 134.3 F g−1 is still maintained at 2 A g−1. Taking into account the aforementioned morphology and textural merits of HPCB-3, such excellent capacitive performances of HPCB-3 is attributed to the synergy of large ion accessible surface area, ideal hierarchical pore structure, and ion-permeable open channels. More concretely, large ion accessible surface area provides enough sites for charge enrichment, ideal hierarchical


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pore structure significantly reduces ion diffusion resistance, and ion-permeable open channels effectively enhances the ion transport kinetics.

Figure 5. (a) Schematic illustration of dual-carbon SIHCs. Electrochemical performances of dual-carbon SIHCs. (b) CV curves at different scan rates. (c) GCD curves at different current densities. (d) Specific capacitance at different current densities. (e) Cycling stability at 1 A g−1. (f) Ragone plots in comparison with other works (inset is the digital photograph of LEDs powered by assembled dual-carbon SIHCs).


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As illustrated in Figure 5a, dual-carbon SIHCs are assembled with HPCS-800 as anodes and activated HPCB-3 as cathodes. As shown in Figure S10, to obtain a device with the optimized electrochemical performance, SIHCs with different active material mass ratios in anode and cathode have been constructed. The longest discharge time of SIHCs with a mass ratio of 1: 2 demonstrates that it possesses the optimized electrochemical performance. Therefore, SIHCs with a mass ratio of 1: 2 is selected for the subsequent tests. Figure 5b, c display the CV and GCD profiles of SIHCs, which can be stably operated at 0.01−4 V. The slight distortion of the CV and GCD profiles should originate from the overlapping effects of two charge storage mechanisms of capacitive processes and intercalation reactions. , CV profile of SIHCs still exhibits an approximate quasi-rectangular shape even at 100 mV s-1 (Figure 5b), indicating an excellent rate capability. Consistently, the GCD profiles of SIHCs (Figure 5c) further indicate a superior rate capability. Figure 5d presents the specific capacitances calculated at different current densities, the SIHCs delivers a specific capacitance of 58.1 F g-1 at 0.1 A g-1, and retains 30.5 F g-1 even at 7.5 A g-1 (52.5% retention). Moreover, the SIHCs retains ≈81% of its initial value even after 4500 cycles at 1 A g−1 (Figure 5e). The significantly enhanced performance of this dual-carbon SIHCs is further demonstrated by comparing the Ragone plot with other recently reported SIHCs (Figure 5f).13,18−20,63−68 This dual-carbon SIHCs can achieve a high energy density of 128.5 Wh kg−1 at the power density of 199.5 W kg−1, and retains 42.6 Wh kg−1 even at an ultrahigh power density of 11.9 kW kg−1. To facilitate application of this dual-carbon SIHCs, we connect one SIHCs to light a “carbon pattern” for at least 5 min, as shown in inset of Figure 5f. The superior properties of the dual-carbon SIHCs can be attributed to four aspects: (1) amorphous carbon frameworks and wide-interlayer of HPCS provide sufficient space for Na+


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insertion/extraction and favorably enhance the energy density; (2) mesopores dominated hierarchical pore structure and a certain degree of N content provide abundant sites for the capacitive behavior, both of these greatly enhance the kinetics behavior of the HPCS anode; (3) choice of optimized hierarchical pore structure and denser packing density HPCB-3 as cathode, the capacitive behavior of which is far superior to most other porous carbon; (4) the dual-carbon SIHCs constructed with similar anodes and cathodes effectively circumvent the kinetics imbalance between anode and cathode. CONCLUSION In summary, we have constructed a novel dual-carbon sodium-ion hybrid capacitor with homologous enhanced kinetics hierarchical porous hollow carbon spheres (HPCS) as the anode and high packing density hierarchical porous hollow carbon bowls (HPCB) as the cathode. The HPCS anode with the integrated advantages of interconnected hierarchical porous structure, a certain degree of N content as well as amorphous carbon frameworks is synthesized through a facile one-pot in-situ template route. Benefiting from these features, the HPCS anode exhibits a superior reversible capacity as well as outstanding rate capability and long-life capability. The HPCB cathode with optimized hierarchical pore structure, denser packing density is fabricated by chemical activation of HPCS, and the symmetrical supercapacitors assembled based on HPCB electrodes exhibit excellent capacitive behaviors. Owing to superior properties and similar microstructure of the anode and cathode, the constructed new dual-carbon SIHCs present an exceptionally high energy/power density (128.5 Wh kg−1 and 11.9 kW kg−1), along with long cycling lifespan. This work opens a new avenue for optimizing the microstructure of hierarchical porous carbon and constructing new type high-performance SIHCs systems. EXPERIMENTAL


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Materials. Tetrapropyl orthosilicate (TPOS), formaldehyde (37 wt %), ethanol, ammonia aqueous solution (25%), 3-aminophenol (3-AP) and hydrofluoric acid (HF) were purchased from Shanghai Aladdin Industrial Corporation. KOH, poly(vinylidene fluoride) (PVDF), N-methyl-2pyrroli-dinone (NMP) and acetylene black were ordered from Sinopharm Chemical Reagent Co., Ltd. All reagents were used as received. Preparation of hierarchical porous hollow carbon spheres (HPCS). 3.46 mL of TPOS was dispersed in a mixture of 70 mL of ethanol and 30 mL of H2O. After the addition of NH3·H2O (3 mL), the mixed solution was stirring for 30 min at 25 °C. Next, 0.5 g of 3-AP and 0.5 mL formaldehyde solution were added into the mixed solution in sequence and keep stirring for 24 h. The intermediates were collected by centrifugation and washed with deionized water. These intermediates were dried at 80 °C and then carbonized under at 800 °C for 5h under argon atmosphere. Finally, HPCS-800 were obtained after removal of silica by HF (10 wt %). For comparison, the same intermediates were carbonized at 700 °C, 900 °C, and 1000 °C, respectively, named HPCS-900 and HPCS-1000. Synthesis of hierarchical porous hollow carbon bowls (HPCB). 200 mg of HPCS-800 powder was first dispersed in 100 mL H2O by ultrasonic treatment for 3 h and then KOH were added into the mixed suspension, the mixed suspension was stirred until forming a homogeneous slurry. After drying in oven at 70 °C, the mixture was calcined at 800 °C for 2 h under argon atmosphere to yield HPCB. Finally, activated products were washed with both a 1 M HCl solution and deionized water to remove residue. The dosages of KOH used in the synthesis of HPCB-x (x = mass ratio of KOH and HPCS-800) were 200 mg, 400 mg, 600 mg, respectively. General Characterization. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were performed on the S-4800, Hitachi and the JEM-2100F, JEOL. Surface


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elemental analysis and functional groups were characterized by X-ray photoelectron spectroscopy (XPS, Thermo Fisher) and Fourier transform infrared spectrometer (Thermo Fisher, FT-IR Nicolet-6700). The structure was analysed by X-ray diffraction (XRD, Rigaku RINT 2200), and Raman spectra were collected on a Raman spectrometer (LabRam HR800). The specific surface area and porous texture were determined using N2 adsorption–desorption (Micromeritics ASAP 2020), calculated by the Brunauer−Emmett−Teller (BET) model and density functional theory (DFT) method, respectively. Electrochemical Measurements. For the fabrication of HPCS anode, working electrodes composed of HPCS, super P, and PVDF in a weight ratio of 3: 1: 1 with NMP as the dispersant. Then the slurry was coated onto Cu foil with designated thickness (200 m), drying at 120 °C for 12 h. For the fabrication of HPCB electrode, 90 wt % HPCB and 10 wt % PVDF were mixed with NMP as the dispersant and then coated on an Al foil. Coin Half cells (CR2032) with sodium wafer as the counter electrode were assembled to test properties of the HPCS anode and HPCB cathode. Dual-carbon SIHCs cells were constructed using HPCS as the anode and HPCB as the cathode, the active material mass ratio of anode and cathode are selected as 1: 1, 1: 2, 1: 3, respectively. Before the assembly of SIHCs, HPCS anode was pre-cycled 3 times in a half cell at 0.1 A g−1. All cells were assembled in an argon-filled glovebox using 1 M NaClO4 in EC/DEC solution (1:1 v/v) with 2 vol % addition of FEC as the electrolyte, glass fibers (Whatman, GF/D) was selected as the separator. CR2032 coin-type symmetric supercapacitors were constructed by using neat EMIM BF4 electrolyte and glass fibers separator to evaluate the capacitive charge storage properties of HPCB. The galvanostatic charge–discharge and cyclic voltammetric tests were performed on the CT2001A test instrument (Wuhan LAND) and CHI 760E (Shanghai Chenhua) electrochemical


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workstation, respectively. EIS tests were performed using CHI 760E workstation (100 kHz to 0.01 Hz) at an amplitude of 5mV. For the half cells tests, the voltage window for the HPCS anode test was conducted under 0.01~3 V while the HPCB cathode test was set as 2.0~4.0 V. For the symmetric supercapacitors cells, the voltage windows were selected as 0~3 V. The voltage window of the Dual-carbon SIHCs cells were set as 0.01~4 V. The specific capacitances of symmetric supercapacitors (C1), HPCB half-cells and full-cells (C2) were calculated according to the following formulas: C1 = 4(IΔt)/(mV) (F g-1)

(3)

C2 = (IΔt)/(mV) (F g-1)

(4)

where I (mA) refer to the current, Δt (s) represents the discharge time, m (mg) indicates the total mass of active materials, and V (V) corresponds to the voltage window excluding ohmic drop. The energy density of symmetric supercapacitors (E1) and full-cells (E2) were obtained from the following formulas: E1 = CV2/(2×3.6×4) (Wh kg-1)

(5)

E2 = CV2/(2×3.6) (Wh kg-1)

(6)

The power density (P) of symmetric supercapacitors and SIHCs were calculated using the following equation formulas: P = 3600×E/t (W kg-1)

(7)

ASSOCIATED CONTENT Supporting Information. SEM images of SiO2@APF colloidal nanospheres, SiO2@HPCS, HPCS, and the transformation schematic diagram of the above three products; Low magnification SEM images of HPCS-800, HPCB; SEM images of HPCS-700, HPCS-900, HPCS-1000; Fourier transform infrared spectra, C1s and O1s high-resolution XPS of HPCS-800


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and HPCB, N 1s high-resolution XPS of HPCS-800; HRTEM images and the corresponding SAED patterns of HPCS, HPCB; Rate capability test of HPCS-700, HPCS-900, and HPCS-1000; SEM and TEM images of HPCS-800 before cycle, after 5000th cycle; Electrochemical performances of HPCB based symmetric supercapacitor in neat EMIM BF4 electrolyte; GCD curves of HPCB at 0.2 A g-1, Electrochemical performance of HPCB-3 cathode; GCD curves of dual-carbon SIHCs at 0.2 A g-1 with different mass ratios; Yield and textual parameters of the HPCS-800 and HPCB; Physical parameters of the HPCS-800 and HPCB; Comparison of the electrochemical performance of reported carbon-based carbon materials for SIBs. The following files are available free of charge. AUTHOR INFORMATION Corresponding Author * Corresponding Author * E-mail: [email protected] Fax: +86 10 64436736; Tel.: +86 10 64436736 * E-mail: [email protected]. Fax: +86 10 64451996; Tel.: +86 10 64451996 * E-mail: [email protected]. Fax: +86 10 64436736; Tel.: +86 10 64436736 Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest.


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ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (Grant No. 51772017 and 51432003) REFERENCES 1. Wang, Y.; Song, Y.; Xia, Y. Electrochemical Capacitors: Mechanism, Materials, Systems, Characterization and Applications. Chem. Soc. Rev. 2016, 45, 5925−5950. 2. Simon, P.; Gogotsi, Y.; Dunn, B. Where Do Batteries End and Supercapacitors Begin? Science 2014, 343, 1210−1211. 3. Ding, J.; Hu, W.; Paek, E.; Mitlin, D. Review of Hybrid Ion Capacitors: From Aqueous to Lithium to Sodium. Chem. Rev. 2018, 118, 6457−6498. 4. Zuo, W.; Li, R.; Zhou, C.; Li, Y.; Xia, J.; Liu, J. Battery-Supercapacitor Hybrid Devices: Recent Progress and Future Prospects. Adv. Sci. 2017, 4, 1600539. 5. Kurra, N.; Alhabeb, M.; Maleski, K.; Wang, C. H.; Alshareef, H. N.; Gogotsi, Y. Bistacked Titanium Carbide (MXene) Anodes for Hybrid Sodium-Ion Capacitors. ACS Energy Lett. 2018, 3, 2094−2100. 6. Gogotsi, Y.; Simon, P. True Performance Metrics in Electrochemical Energy Storage. Science 2011, 334, 917−918. 7. Ding, J.; Wang, H.; Li, Z.; Cui, K.; Karpuzov, D.; Tan, X.; Kohandehghan, A.; Mitlin, D. Peanut Shell Hybrid Sodium Ion Capacitor with Extreme Energy–Power Rivals Lithium Ion Capacitors. Energy Environ. Sci. 2015, 8, 941−955. 8. Aravindan, V.; Gnanaraj, J.; Lee, Y. S.; Madhavi, S. Insertion-Type Electrodes for Nonaqueous Li-Ion Capacitors. Chem. Rev. 2014, 114, 11619−11635.


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Homologous Hierarchical Porous Hollow Carbon Spheres Anode and

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