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N/P co-doped porous carbon/one-dimensional hollow tubular carbon heterojunction from biomass inherent structure for supercapacitors Li Li, Yanmei Zhou, Hua Zhou, Haonan Qu, Chengli Zhang, Meixia Guo, Xiaoqiang Liu, Qingyou Zhang, and Bin Gao ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b05022 • Publication Date (Web): 20 Nov 2018 Downloaded from http://pubs.acs.org on November 21, 2018

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ACS Sustainable Chemistry & Engineering

N/P co-doped porous carbon/one-dimensional hollow tubular carbon heterojunction from biomass inherent structure for supercapacitors Li Li,a Yanmei Zhou,*a Hua Zhou,a Haonan Qu,a Chengli Zhang,a,b Meixia Guo,a Xiaoqiang Liu,a Qingyou Zhanga and Bin Gaoc a

Henan Joint International Research Laboratory of Environmental Pollution Control Materials,

College of Chemistry and Chemical Engineering, Henan University, Jinming Avenue, Kaifeng, Henan 475004, China b The

college of Environment and Planning, Henan University, Jinming Avenue, Kaifeng, Henan

475004, China c

Department of Agricultural and Biological Engineering, University of Florida, Gainesville,

Florida 32611, United States Corresponding author: Tel: +86-371-22868833-3422; Fax: +86-371-23881589 E-mail address: [email protected] (Yanmei Zhou)

ACS Paragon Plus Environment

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ABSTRACT: A N/P co-doped porous carbon/one-dimensional (1D) hollow tubular carbon heterojunction was successfully fabricated from waste biomass. 1D carbon microtube (CMT) originating from the inherent biological structure of enteromorpha prolifera (EP) was used for constructing the heterojunction with uniform heteroatom distribution and good conductivity by pyrolyzing the chitosan dihydrogen phosphate protic salt (CDPPS) coated CMT, in which CMT was used as conductive substrate and CDPPS as carbon, nitrogen, phosphorus sources and “soft” activating agent. The optimized heterojunction (NPEPC-6-900) possesses a large specific surface area (1220 m2 g–1) and high content of heteroatom functionalities (4.50 at% N and 2.36 at% P). A similar effect also occurs on cotton with analogous 1D hollow tubular architecture structure, and the sample presents a specific surface area (766 m2 g–1) and chemical composition (3.75 at% N and 1.34 at% P). Benefiting from the distinctive structural feature and desirable heteroatom doping, the NPEPC-6-900 based electrode indicates high capacitance of 324 F g–1 at 1 A g–1, and still maintains the capacitance of 231 F g–1 even at 20 A g–1 (ca. 71.3% capacitance retention). Moreover, it also possesses good cycling stability with only a loss of 2% after 5000 cycles.

KEYWORDS: 1D hollow carbon microtube; heterojunction; chitosan phosphate protic salt; N/P co-doped porous carbon; biological structures

INTRODUCTION Supercapacitors hold great promise in scientific researches, owing to their high power density, ultra-fast charge/discharge rate, superior stability, long cycle life and safe operation.1-10 Carbonaceous materials play essential parts in this field, some of which could be put down to the advisable chemical composition and diversiform microtexture features.11-15 In this context, heteroatom (e.g., N, P, B and S) doping has been proven to be a promising method to remarkably


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improve the electrochemical performance. The electronic structure, atomic radius and electronegativity of heteroatoms are different from those of carbon atoms, which not only introduce energy defect sites on the surface of material, but also modulate the electron donoracceptor characteristics.5, 16-19 Thus, the N/P co-doped carbon materials have been investigated to obtain higher electrochemical properties through improving the wettability in the electrolyte, increasing the electrical conductivity, introducing mixed pseudocapacitance and widening the potential window.16, 20-24 Furthermore, the carbon materials with one-dimensional (1D) hollow structure, such as carbon fibers and carbon microtubes, not only ensure adequate contact area between the active sites and the electrolyte but also possess efficient pathway for ion and electron transport, thus obtaining excellent-performance supercapacitors.25-29 Taking the above things into account, it is greatly advisable to construct N and P co-doped 1D hollow carbon materials as supercapacitor electrode materials. Nevertheless, the reported porous carbon materials always consume high-priced production cost which seems daunting for a large-scale preparation, thus low cost biomass-derived carbon materials have emerged.30, 31 It is rather remarkable that biological structures (e.g., woods, fish scale) evolved from the natural selection process normally exhibit a host of architectural features with delicate control of architecture hierarchy and composition from microscopic scale to macroscopic scale.32 When prepared as electrodes for supercapacitors, the special structure of these materials is advantageous for capacitive performance, such as willow catkin-derived Ndoped hollow hierarchical porous carbon microtubes reveal 292 F g–1 at a current density of 1 A g–1,33 dandelion fluff-derived carbon tube bundle electrode displays a high specific capacitance of 355 F g–1 at 1 A g–1.34 However, the making process of these porous materials is always employing chemical reagent (e.g., potassium hydroxide, zinc chloride and potassium bicarbonate) as


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activation agents.35 Summarily, high-performance porous carbon electrode materials can be prepared using these methods but generally receiving low carbon yields, and the heavy use of traditional corrosive activating agents will place a great burden on environment. Additionally, subsequent acid and water washing procedures make the entire fabrication process tedious and time-consuming. It is highly desired to design a simple and environmentally benign way that avoids the use of accustomed activating reactants to fabricate biomass-derived porous materials without destroying the biomass original structure. Furthermore, biomass containing multifarious elements can be used as dopants in pyrolyzed carbon. However, due to the fact that the element species and content is quantitative and meagremean, it cannot meet the needs of high-performance electrode materials. For these issues, biomass-derived N/P doped heterojunction with tunable heteroatom content synthesized without using traditional corrosive activating agents should be noticed. The green tides from booming of enteromorpha prolifera (EP) cause bad impressions on marine ecosystem, coastal farming, ocean transportation and tourism.36, 37 Thus the rational use of EP became a challenge and the microtubular structure of EP made it possible to convert to 1D porous carbon materials.38 As is known, chitin and its derivative chitosan are the amplest and cheapest biomass resources with abundant nitrogen content.39 Chitosan dihydrogen phosphate protic salt (CDPPS), coming from one-step ordinary neutralization of phosphoric acid with aminogroup in chitosan, can be studied as a potential carbon precursor with thermal stability, porosity and regulatable heteroatom content at the molecular level.40-43 In this work, we combined the synergistic effects of special 1D structure and adjustable heteroatom doping content, thus designing an exercisable approach to synthesis all biomassderived 1D N/P co-doped carbon microtubes (denoted as NPCMTs). EP-derived carbon microtube


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(CMT) was used as the conductive substrates, whilst CDPPS was employed as carbon source, nitrogen and phosphorus source as well as porogen. In addition, it is noteworthy that the heteroatom content could be regulated by changing the ratio of CDPPS and CMT. Moreover, cotton as the purest source of cellulose whose distribution was the most extensive and content was the largest with intertwined millimeter-scale cellulose fibers was also applied as 1D conductive backbones to prepare NPCMTs.28, 29, 44 Benefiting from unique 1D hollow porous structural feature, large specific surface area (SSA), good conductivity and high N/P-doping level, these NPCMTs deliver preeminent properties as supercapacitor electrode materials with high specific capacitance, long-term cycling stability and excellent energy density. EXPERIMENTAL SECTION Preparation of carbon microtubes (CMTs) CMTs were prepared as reported in the literature.29, 38 EP was firstly pretreated to obtain the EP aerogel. CMTs were prepared by pyrolyzing the respective EP aerogel at 700 °C or cotton at 800 °C, which were denoted as EPC or CF. Preparation of CDPPS and NPCMTs The CDPPS was prepared according to our previous work.45, 46 1.6 g chitosan was dissolved in 50.0 mL deionized water (add small amount of acetic acid to assist dissolution) under gentle agitation. Subsequently, 6.7 mL dilute phosphoric acid (1.5 M) was added dropwise with an ice bath, upon further stirring for 2 h at room temperature. Afterwards, 0.1 g EPC was completely immersed into above solution under vacuum for 4 h. The EPC@CDPPS-x composite (x = 4, 6 and 8, x represents the mass ratio of CDPPS to EPC) was fabricated by curing at 160 °C for 12 h. The


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resultant composite was calcinated under N2 atmosphere at 400 °C for 2 h with a heating rate of 2 °C min–1, and subsequently heated to a certain temperature with a heating rate of 5 °C min–1 for 2 h. The final product was nominated as NPEPC-x-y (x is mentioned in the EPC@CDPPS-x composite; y = 800, 900 and 1000, y denotes the carbonization temperature). NPCF-x-y was obtained under the same experimental condition. For comparison, the EPC, CF and CDPPS were pyrolyzed at 900 °C, which were nominated as EPC-900, CF-900 and PS-900. RESULT AND DISCUSSION Morphology and structure Scheme 1 schematically illustrates the synthetic approach of NPCMTs using biomass-derived CMTs as the conductive skeleton and CDPPS as the N and P-content coating layer precursor. Initially, pre-carbonization of EP was converted it into CMT as the conductive substrates. Secondly, CDPPS and substrates were combined through cation-π interaction to form a jarless gauzy coating that guaranteed uniform surface modification of complex materials.47 Moreover, in the carbonization process, the N and P-rich CDPPS coating not only was converted to N/P uniformly distributed carbon layer that was coated on the CMT, but the CDPPS itself also produced a mainly microporous carbon probably owing to the similar activation effect of the [H2PO4] anion with phosphoric acid.41 In addition, this process also applies to cotton. All these properties boost the formation of a filmy N/P co-doped porous carbon layer overlaid on the CMTs surface, thus fabricating the all biomass-derived, no traditional corrosive activating agents participated, N/Pdoped porous carbon/1D hollow tubular carbon heterojunction.


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Scheme 1. Schematic illustration of fabrication process of the NPCMT. FTIR spectroscopy was employed to demonstrate the successful synthesis of the CDPPS (Figure S1b). Compared with the spectrum of chitosan, the strong broad absorption band in the range of 2996–3244 cm–1 in CDPPS is attributed to the symmetrical and asymmetrical stretching vibrations of NH3+ group, which indicates the successful protonation of amino groups in chitosan. Like the characteristic peak of P–O in the spectrum of NH4H2PO4, the absorption peak at 947 cm–1 in CDPPS spectrum is ascribed to the stretching vibration of P–O bond while the peak at 512 cm–1 is attributed to the formation vibration of P–O bond in the spectrum of CDPPS.48 The morphologies of the whole samples were investigated via SEM. The microtexture of the EPC-900 and CF-900 both display hollow microtubular structure (Figure 1a–c and Figure 1d, e), which has been inherited from the original EP and cotton microtube. And the diameter of the EP-derived microtube is about 30–50 μm, whlie the diameter of the cotton-derived microtube is about 10–20 μm.29, 38 After CDPPS coating (CDPPS/CMT = 6) and high temperature calcination (900 °C), the hollow and tube structures still can be observed in NPEPC-6-900 and NPCF-6-900 (Figure 1f–h


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and Figure 1i, j), demonstrating the unique structure perfectly preserved. In addition, it is clear that structural variations also can be noticed. Porosity and folds on the surface of NPEPC-6-900 (Figure 1g, h) can also be seen, in contrast, the SEM image (Figure 1b, c) of EPC-900 shows a relatively smooth surface without apparent pores. The same phenomenon also appears in the comparison between NPCF-6-900 (Figure 1j) and CF-900 (Figure 1e). An analogous 1D hollow microtube structure is also apperceived in NPEPC-6-800, NPEPC-4-900 and NPEPC-8-900 (Figure S2a, c, d). The porous tube structure can ensure superior electron transport along its ultralong 1D backbone and possess large inner diameter for plenitudinous electrolyte permeation, which can enable fast electron and ion transport.34 However, with the increased calcination temperature (1000 °C), the hollow tubular microstructure is damaged (Figure S2b). EDX maps of NPEPC-6-900 (Figure 1k–m) and NPCF-6-900 (Figure 1n–p) demonstrate the evenly distribution of N and P elements on the surface of the material, confirming the successful coating of CDPPS onto carbon skeleton. The TEM images of the NPEPC-6-900 (Figure 1q) and NPCF-6-900 (Figure 1r) further confirm N/P co-doped carbon layer successfully coated on the CMTs, thus indicating the formation of N/P co-doped porous carbon/carbon heterojunction.


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Figure 1. The SEM images with different magnification: (a–c) EPC-900, (d, e) CF-900, (f–h) NPEPC-6-900, (i, j) NPCF-6-900; EDX maps of (k–m) NPEPC-6-900 and (n–p) NPCF-6-900; TEM images of (q) NPEPC-6-900 and (r) NPCF-6-900. The crystallinity and composition of carbon materials are also crucial for their performance as electrode materials for supercapacitors.21 XRD was tested to investigate the crystallinity (Figure 2a and Figure S3a). All the samples display the two distinctive broad peaks with low intensities centered at around 24° and 44°, correspond to (002) and (100) diffraction planes, disclosing that the whole samples have low graphitization degrees.6, 7, 49 The (002) diffraction peaks for NPCMTs show left shifting compared with the EPC-900 and CF-900, implying larger interlayer spacing of the (002) plane of these NPCMTs. The phenomenon may be deemed to catalytic distortion of the graphitic plane caused by N and P doping.16 The degree of graphitization of the samples was further identified by Raman spectroscopy (Figure 2b and Figure S3b). The D band at ca. 1340 cm–1 and G band at ca. 1590 cm–1 assigned to the disordered carbon or defects in hexagonal lattice and the ordered sp2 carbon, respectively.13, 50 In general, the ratio of intensities (ID/IG) can be calculated to indicate the degree of structural disorder. The values of the EPC-900 and CF-900 are distinctly lower than NPCMTs, which can be attributed to the introduction of N and P elements resulting in more edges and surface defects.15, 16 And the value of ID/IG increases in the order of NPEPC-8-900 (1.04) > NPEPC-6-900 (1.03) > NPEPC-4-900 (0.98) (Table S2), implying that the amount of disordered carbon or edge defects increases with incremental heteroatom content.51 Besides, the calcination temperature also affects the degree of graphitization, as shown in NPEPC-6-800 (1.06), NPEPC-6-900 (1.03), NPEPC-6-1000 (0.96) (Table S2), confirming that higher temperature will lead to an enhancement of graphenic order.52


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Figure 2. (a) XRD patterns and (b) Raman spectra of the EPC-900, CF-900, NPEPC-6-900 and NPCF-6-900; (c) N2 adsorption/desorption isotherms and (d) the pore size distributions of the EPC-900, NPEPC-4-900, NPEPC-6-900 and NPEPC-8-900. The chemical composition of the NPCMTs with various doping ratios was measured by XPS, and the homologous survey spectra and the results of spectroscopic analysis are provided in Figure 3 and Table S1.53 The peaks centered at 401 eV and 134 eV in all spectra of the four NPCMTs samples corresponding to N1s and P2p energy levels reveal the effectual incorporation of N and P into NPCMTs (Figure 3a), which is also consistent well with the EDX maps analysis. According to the literatures,29, 38 the CMTs from pretreated EP and cotton only contain C and O elements rather than N and P elements, thus elucidating the doped heteroatoms should be originated from


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the CDPPS. As shown in Table S1, with the increasing mass ratio of CDPPS/CMTs, the N and P content are increased in succession, and the highest doping contents of 5.51 at% N and 2.82 at% P are presented in NPEPC-8-900. Based on this conclusion, it is worth noting that we could achieve molecular level control of heteroatom doping by adjusting the protic salt doping ratio. Specifically, NPEPC-6-900, in which the element percentage of C, O, N and P is estimated to be 78.93, 14.21, 4.50 and 2.36 at%, is discussed with N and P configurations in detail. The high-resolution N1s XPS spectrum (Figure 3b and d) is deconvoluted into four components: pyridinic N (N-6, 398.4 eV, 11.9%), pyrrolic N (N-5, 399.9 eV, 27.9%), quaternary N (N-Q, 401.2 eV, 50.7%) and oxidized N (N-X, 403.0 eV, 10.4%).46, 53 N-Q is the dominant constituent due to N-Q is more stable at high temperature.54, 55 N-5 and N-6 could provide additional free electrons or delocalized electrons to the conduction band, whereas N-Q and N-X can supply higher electronic conductivity and faster electron transfer.56 For phosphorus, the P2p spectrum (Figure 3c) demonstrates the existence of two deconvoluted peaks, where the one centered at 132.8 eV assigned to P–C bond and the other centered at 133.6 eV corresponding to P–O bond.52, 57, 58 The analysis results reveal that the P atoms are incorporated into the carbon framework. And the deconvoluted spectra of NPEPC-4-900, NPEPC-8-900 and NPCF-6-900 were researched in Figure S4–6.


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Figure 3. (a) XPS survey spectra of the NPEPC-4-900, NPEPC-6-900, NPEPC-8-900 and NPCF6-900; deconvoluted XPS spectra of the NPEPC-6-900 (b) N1s, and (c) P2p; (d) the content and types of N in NPEPC-4-900, NPEPC-6-900, NPEPC-8-900 and NPCF-6-900. It is well known that large specific surface area and suitable pore size distribution play a significant role in improving the capacitive performance of materials. The porous texture of EPC900, NPEPC-4-900, NPEPC-6-900, NPEPC-8-900 and NPCF-6-900 was examined through nitrogen adsorption/desorption measurements. The extraordinary low N2 uptake of EPC-900 and CF-900 reveals that there is nearly nonporous in the CMTs without CDPPS addition (Figure 2c).29 Distinctly, the large specific surface area (753–1220 m2 g–1) can be put down to the efficacious activation of CDPPS. These isotherms of the NPEPC-4-900, NPEPC-6-900, NPEPC-8-900


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(Figure 2c) and NPCF-6-900 (Figure S7) display the same characteristics of the intermixed type I and IV isotherm, with a BET specific surface area of 753, 1220, 1206 and 766 m2 g–1, severally. The sharp adsorption slope at P/P0 < 0.1 shows scores of micropores, whilst the parochial hysteresis loop appeared in the higher P/P0 manifests a minute amount of mesopores. The pore size distribution curves also reveal the concomitant of micropores and mesopores, like NPEPC-6900 sample shows microspores with peaks centered at 0.52–0.64, 0.82 and 1.2 nm and mesopores with peaks located at 2.2 nm. This porosity and textural characteristic of NPCMTs are profitable to employing as high-performance supercapacitor electrode materials, in which micropores provide rich sites as locations for charge accumulation and mesopores as channels for shortening the ion diffusion distance whilst 1D hollow microtube can serve as reservoirs to buffering electrolyte ions. Supercapacitor performance


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Figure 4. Electrochemical performance in three-electrode setup: (a, d) CV curves at a scan rate of 50 mV s–1; (b, e) variation of the specific capacitances calculated from the discharge curves at different current densities; (c, f) Nyquist plots with the close-up view on the high-frequency region. Benefiting from the 1D hollow microtube structure and regulatable N and P dopants, the activated carbon materials with high specific surface area and suitable pore size distribution are expected to be the probable electrode material for supercapacitors. The electrochemical performance of the whole specimens was systematically evaluated using a three electrode configuration, with 6 M KOH as the electrolyte solution. To evaluate the distinctive structural property and the possible effect of heteroatom doping on supercapacitive performance, the cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and electrochemical impedance spectroscopy (EIS) curves of the EPC-900, CF-900, PS-900, NPEPC-6-900 and NPCF-6-900 were carried out and summarized respectively. Figure 4a compares the CV profiles of these five kinds of samples measured at a scan rate of 50 mV s–1. Compared with the quasi-rectangular shapes in EPC-900 and CF-900 samples, the CV curves of NPEPC-6-900 and NPCF-6-900 illustrate not only quasi-rectangular shapes but also broadened peaks stemmed from the redox reactions of N and P-containing groups, demonstrating the coexistence of both electric double layer capacitance and pseudocapacitance. In comparison, the control specimens of the EPC-900, CF-900 and PS900 show a smaller encircled area, and thus, a lower capacitance, than that of the complex carbon materials. GCD measurement was also conducted to investigate the electrochemical properties (Figure S8), the gravimetric capacitances of NPEPC-6-900 and NPCF-6-900 are 324 and 271 F g–1 at 1 A g–1, whereas the capacitances of EPC-900 and CF-900 are 173 and 168 F g–1. This is because satisfactory chemical composition and large surface area as well as ideal pore structure play a vital part in electrochemical performance.25 As shown in Figure 2d, the NPCMTs all have


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micropores (about 0.5–0.6, 0.8 and 1.2 nm) and small mesopores (about 2.2 nm), in which micropores could act as active sites to provide the hydrated K+ (0.362–0.42 nm) adsorption for the formation of electric double layer and mesopores can facilitate the rapid diffusion and transport of ions through shortening the transport distance.4, 10 Thereto, NPEPC-6-900 and NPCF-6-900 also have larger capacitances than PS-900 (195 F g–1 at 1 A g–1 ), which is attributed to the unique 1D hollow structures offering efficient pathway for ion and electron transport. As displayed in the Nyquist plots (Figure 4c), in the low-frequency region, a nearly parallel line to the imaginary axis for the no heteroatom-doped EPC-900 and CF-900 electrodes reveal an ideally capacitive behavior due to the non-faradaic charge storage mechanism.7 Whereas both NPEPC-6-900 and NPCF-6900 electrodes show inclined curves, suggesting the contribution of pseudocapacitance from N and P incorporation.44 In the high-frequency region, the diameter of the semicircle represents the charge transfer internal resistance (Rct). PS-900 has a higher Rct value than NPEPC-6-900 and NPCF-6-900, proving that the complex NPCMTs electrodes enjoy profitable charge-transfer kinetics because of the highly conductive tubular scaffold.44 Moreover, the Rct value for NPEPC6-900 and NPCF-6-900 are distinctly lower than the no heteroatom-doped EPC-900 and CF-900, which can be ascribed to the porous and folds structure and good wettability caused by heteroatom doping.59 Through all the above electrochemical performance comparison, it is noted that the method of preparing porous heteroatom-doped composite heterojunction as supercapacitor electrode material is very desirable, in which we use the 1D carbon microtube originated in the biomass biological structures as a conductive skeleton and the protic salt derived from waste biomass as carbon source, nitrogen source, phosphorus source and porogen. We also explored the effect of different calcination temperature and doping ratio on the electrochemical performance of the composite materials. The NPEPC-6-900 electrode own the


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best electrochemical performance among the five specimens, manifesting CV profiles with the largest current density at the same scan rate, together with the highest discharge time in GCD plots and the lowest equivalent series resistance (ESR) shown in the Nyquist plots (Figure 4d,f, and Figure S8b). As for the impact of calcination temperature, NPEPC-6-900 exhibits a large specific capacitance up to 324 F g–1 (at 1 A g–1), which is higher than those of NPEPC-6-800 (277 F g–1) and NPEPC-6-1000 (221 F g–1). This may be because protic salt porogen generally exhibits a large number of pores at a higher calcination, but the pores cannot be completely generated at a lower temperature of 800 °C.42 Additionally, the microstructure of the 1D conductive hollow structure is destroyed at 1000 °C (can be observed in Figure S2b). Interestingly, we found that the heteroatom content and the specific surface can be controlled accordingly with the different amount of protic salt. The specific capacitances calculated from GCD curves are 220, 324 and 271 F g–1 at 1 A g–1 of NPEPC-4-900, NPEPC-6-900 and NPEPC-8-900, respectively (Figure S9). Among them, NPEPC-6-900 possesses the largest specific surface area and the most reasonable pore size distribution, albeit NPEPC-8-900 owns the highest heteroatom content, thus indicating the most excellent electrochemical performance of the NPEPC-6-900. The CV and GCD curves of NPEPC-6-900 were revealed in Figure 5a and b. All CV curves display approximately rectangulare shape with blatant humps, informing the complete capacitance primarily originating from the electric double layer capacitance and an auxiliary of the pseudocapacitance. In order to further confirm the excellent charge storage ability of the NPEPC6-900 based electrode, the GCD measurement was carried out at the current densities from 1 to 20 A g–1. The curves all display isosceles triangular shapes attributed to the electric double layer capacitance and a slight bending coming from the pseudocapacitance effect of N and P doping, which correlates with the rectangular-like shape and humps in the CV curves. Rate capability is


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also a key factor for supercapacitors in practical applications, NPEPC-6-900 still retains a high specific capacitance (up to 231 F g–1) even at 20 A g–1 with 71.3% retention rate (Figure 4e), revealing wonderful rate properties compared with other heteroatom-doped electrodes (Table S3). Meanwhile, NPEPC-6-900 also holds the superior cycling durability (Figure 5c) by showing 98% of initial capacitance after 5000 cycles, stating a highly reversible charge/discharge process. Through the above comparison test, the remarkable electrochemical properties of NPEPC-6-900 can be summarized as three aspects (Figure 5d): firstly, the 1D hollow structure guarantees adequate contact area between the active sites and the electrolyte, as well as possesses efficient pathway for ion and electron transport; secondly, the N and P incorporation in a carbon network alters the electronic band structure, thus enhancing the capacitive performance through improving the wettability and engendering the reversible faradaic process,20-22 the P doping can widen the potential window due to enhanced oxidation stability to raise the energy density additionally;16, 23, 24

thirdly, a high SSA can provide abundant sites as the locations for charge accumulation and the

ideal pore structure mainly ensure excellent electrochemical kinetics.25,

46

In consequence,

compared with other biomass derived previously reported carbon materials as supercapacitor electrodes, NPEPC-6-900 is very competitive, as shown in Table S4.


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Figure 5. Electrochemical performances of the NPEPC-6-900 electrode in three-electrode setup: (a) CV curves versus different scan rates; (b) GCD curves versus different current densities; (c) cycling performance by repeating CV at 100 mV s–1; (d) the schematic diagram of the advantages of the NPCMTs employed as supercapacitor electrode materials. To meet the practical application requirements, the electrochemical properties of NPEPC-6900 based electrodes were also investigated in a symmetrical two-electrode supercapacitor in 6 M KOH. The CV curves with different operating potential windows were detected as shown in Figure 6a. It is clearly seen that the stability potential window of the device is about 1.3 V based on the box-like shape of CV curves.60 To further verify the wide stable voltage window, CV profiles at different sweep rates (Figure 6b) as well as its GCD curves measured at different current densities (Figure 6c) all employed in this potential window. It is well noted that P doping can improve the stability of carbon electrodes in the aqueous electrolyte, thus expanding the voltage window. The quasi-rectangular shape of the whole CV curves promulgates favorable rate performance and the symmetric triangle shape of the GCD profiles reveals excellent reversibility of the electrode.34 The specific capacitance of NPEPC-6-900 is 174 F g–1 at a current density of 0.5 A g–1. Moreover, the energy density of NPEPC-6-900 is up to 10.2 W h kg–1 at a power density of 163.4 W kg–1 (Figure 6d). Compared to previously reported symmetrical supercapacitors assembled by biomass-derived carbon materials with 6 M KOH as electrolyte, the supercapacitor reported in this work exhibits excellent energy density and power density.21,

61-68

The two as-assembled symmetrical

supercapacitors connected in series can apply as an efficacious energy supplier for electronic devices, as shown in Figure 6e, the tandem device can light up a red LED bulb brightly for more than 5 min.


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(e)

Figure 6. Electrochemical performances of the NPEPC-6-900 based symmetric supercapacitor with 6 M KOH electrolyte: (a) CV curves in different operation voltages at 50 mV s–1; (b) CV curves versus different scan rates; (c) GCD curves versus different current densities; (d) Ragone plots of the symmetrical supercapacitor and performance comparison with the literatures; (e) optical images of a red LED bulb brightly powered by two symmetrical supercapacitors in series at 0 and 5 minutes. CONCLUSIONS A “soft” activating agent was synthesized to fabricate N/P co-doped porous carbon/1D hollow tubular carbon heterojunction derived from waste biomass (EP and chitosan) for high-performance supercapacitors. With the large ion-accessible surface area, efficient electron and ion transport pathways from the idiographic 1D hollow tubular architecture structure and rich porosity along


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with abundant N and P content from waste biomass-derived protic salt, the EP-derived heterojunction displays a high capacitive performance (324 F g–1) and high power density (10.2 W h kg–1) together with excellent rate capability (71.3%) and cycling stability (98% capacity retention after 5000 cycles). We also attempt that the green and effective strategy can be extended to cellulose with 1D hollow tubular cellulose fibers, such as cotton, still obtaining high-performance electrode materials. It is indicated that biomass with 1D hollow tube can apply as effective conductive backbones that can construct complexes with other precursors acting as both heteroatom sources and novel activation agents, fabricating heterojunction with large specific surface area and controllable compositions, which can supply a guidance to design low-cost, all biomass derived porous carbon materials with distinctive structural feature from biomass inherent structure and tunable heteroatoms doping for supercapacitors. ASSOCIATED CONTENT Supporting Information. The characterization, electrochemical measurements, FTIR spectra, SEM images, XRD patterns, Raman spectra, deconvoluted XPS spectra, N2 adsorption/desorption isotherms, GCD curves, porosity parameters, elemental composition, ID/IG values, summary of the specific capacitances of reported carbon materials supplied as Supporting Information. AUTHOR INFORMATION Corresponding Author *E-mail address: [email protected] Notes The authors declare no competing financial interest.


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ACKNOWLEDGMENT The authors thank the National Natural Science Foundation of China (21776061, 21576071 and U1504215), the program for Science & Technology Innovation Team in Universities of Henan Province (19IRTSTHN029), the program for Science & Technology Innovation Talents in Universities of Henan Province (19HASTIT037) and the Foundation of International Science and Technology Cooperation of Henan Province (162102410012).

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For Table of Contents Use Only

Synopsis Biomass-derived N/P co-doped one-dimensional hollow tubular porous carbon heterojunction was fabricated by a low-cost and green method for high-performance supercapacitors.


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one-dimensional hollow tubular carbon

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