Absorption of Three-Dimensional

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Superb Electrolyte Penetration/Absorption of 3D Porous Carbon Nanosheets for Multifunctional Supercapacitor Xianbin Liu, Changgan Lai, Zechen Xiao, Shuai Zou, Kaixi Liu, Yanhong Yin, Tongxiang Liang, and Ziping Wu ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.9b00002 • Publication Date (Web): 12 Apr 2019 Downloaded from http://pubs.acs.org on April 14, 2019

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ACS Applied Energy Materials

Superb Electrolyte Penetration/Absorption of 3D Porous Carbon Nanosheets for Multifunctional Supercapacitor Xianbin Liu*, Changgan Lai, Zechen Xiao, Shuai Zou, Kaixi Liu, Yanhong Yin, Tongxiang Liang, Ziping Wu* School of Materials Science and Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, P. R. China * Corresponding author. E-mail address: Xianbin Liu, [email protected] or [email protected] Ziping Wu, [email protected]

Abstract High specific surface area and reasonable pore-size distribution are conducive to promote the energy density and power density of carbon based supercapacitors. Nevertheless, the permeability of electrolyte is prerequisite condition for surface storage charge and the ion diffusion in multi-scale pores. Therefore, improving the electrolyte penetration/absorption shows particularly important. Herein, we reported a novel three-dimensional porous ultrathin carbon nanosheet (3DPAC) with considerable electrolyte penetration/absorption property, which was proved by experiment and theory. The 3DPAC was prepared from abundant biomass waste wood dust via hydrothermal and carbonized treatment, and characterized with ultrathin nanosheets, abundant porous structure and rich N, O dopant. This unique 3D and hierarchical porous structure leads to robust the conduction of electrons and the penetration/absorption of electrolyte ions, which endow the 3DPAC with approving electrochemical properties. The supercapacitor based 3DPAC shows satisfying energy density (79.4 Wh/kg) and power density (5.1 kW/kg), and impressive cyclic stability with 94.6 % after 5000 charge/discharge processes. More amazing, the soft-packaged supercapacitor presents stable electrochemical behaviors at multiple folding states and low pressure environment. Therefore, this meaningful research will open a bran-new direction to devise and prepare state-of-art porous carbon materials for high-performance supercapacitors applied in complex environments.

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Keywords 3D

structure;

amorphous

sheets;

electrolyte

penetration/absorption;

Supercapacitor;

Environmental suitability

1. Introduction Along with the fast development of modern science and technology, all kinds of portable intelligent electronic wearable devices appeared, and the electronic equipment gradually to develop in the direction of miniaturization, planarization, flexibility and so on, even to special circumstances, such as folding, pressure and pull. The vital to the development of the multifunctional electronic devices requires compatible energy storage devices, which not only have the long cruising ability, more importantly are able to maintain steady working in the special conditions.[1-3] Owing to their fast charge/discharge processes, superior power delivery and prominent cycling stability, supercapacitors have attracted extensive attentions with the increasing demand of clean and sustainable energy technologies.[4-7] According to the mechanism of energy storage, supercapacitors generally can be classified into two categories: electrochemical double-layer capacitors (EDLCs) and pseudocapacitors. Over a long time, porous carbon has been widely regarded as idea active materials for supercapacitor attributing to its outstanding characters including high electrical conductivity, large surface area, favourable physical and chemical stability.[8-10] However, the present supercapacitors based single carbonaceous materials suffer from low energy density (4-10 Wh kg-1) due to the limitations of their energy storage mechanism and environmental constraints without folding or pressing, which limit their widespread applications in the future.[2

11]

To cater next generation highly efficient supercapacitors for the

fast-growing energy demands, it is urgent need to develop flexible electrodes based on advanced nano carbon to improve the energy density and environmental suitability. To date, both experimental and theoretical results reveal that the multiple-scale pores in carbon material are beneficial to ion diffusion, which is fundamental factor to the large capacitance and high rate. As early as 2010, Black et al. have used a transmission line model to simulate charge-transfer mechanism of different pore sizes and concluded that multi-scale pores are favorable for charge diffusion.[12] Afterwards, Ervin has discovered that wide aperture distribution can promote ion accumulation in a single layer graphene film.[13] Latest, Yat et al have


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synthesized a three-dimensional (3D) carbon materials featured with multi-scale pores and demonstrated the hierarchical porous structure containing micro-, meso-, and macropores could accelerate high-efficient ion diffusion and electron transmission. [14] However, the permeability of electrolyte is prerequisite condition for surface storage charge and the ion diffusion in multi-scale pores. Besides the increasing of active sites, heteroatoms doping is beneficial to improve the permeability of electrolyte.

[15-20]

Inducing nitrogen (N) and oxygen (O) have been shown to

enhance the interaction between electrolytes and active carbon materials, leading to fast permeation and vast storage. On the other hand, the microstructures of materials also affect their permeability.

[21-25]

The amorphous carbon with defects and voids are attributed to the ions

permeation. Ouassim investigated the microstructural effects on charge-storage characteristics based on MnO2 and discovered that the amorphous MnO2 (birnessite) showed better electrochemical performance relying on the ionic conductivities.[26] Yu et.al have synthesized a 3D amorphous carbon sheets with disordered and porous structures via a facile NaCl template-assisted method, the increased disordered structures can not only promote the diffusion of Na+ ions but also improve the reversible capacity of Na storage.[27] Moreover, Chen et.al have investigated the mechanism of electrolyte infiltration affecting the energy storage characteristic based on lithium–sulfur batteries.[28] Therefore, it is significant to achieve the superb electrolyte penetration/absorption. For ideal flexible carbon-based electrodes, specific surface area directly affects the amount of charge stored on the surface of electrode materials.[29-32] Two dimensional (2D) carbon materials can balance the contradiction between electrical conductivity and specific surface area of carbon in view of its large surface area independent of the pore structure.[33-37] Importantly, for electrochemical applications, the whole carbon surfaces could be exposed to the electrolyte and can take part in charge storage in such 2D nanomaterials. On the other hand, engineering of hierarchical pores in the carbon materials optimize porosity for facilitated ion transport. Therefore, great efforts have been devoted to design customized carbon materials with optimized structural characteristics for supercapacitor electrodes by increasing specific surface area and optimizing pore architecture such as constructing reasonable 3D network structure with 2D carbon nanosheets,.[38-41] Inspired by the aforementioned achievements, herein we synthesized a three-dimensional



porous carbon nanosheets (3DPAC) material accompanied with heteroatoms doping from biomass waste wood dust via hydrothermal and carbonized treatment, and the resultant 3DPAC exhibits a graphene-like nanosheet unit and frame network structure, leading to a high specific surface area (2034 m2/g) and a relatively low pore size (4.09 nm). The combination of hydrothermal and carbonized treatment is conducive to the doping of heteroatoms and the regulation of pore structure. Therefore, the doping amounts of N and O in the carbon nanosheets are 6.1 % and 7.9 %, respectively. Thus the 3DPAC was endowed with superb electrolyte penetration/absorption. Accompanied by the multi-scale pores structure, the 3DPAC electrode exhibits high specific capacitance of 421 F/g at 1 A/g and favorable rate capability of 80 % at 50 A/g, which are better than those of trGO. Furtherly, the symmetrical supercapacitor based on 3DPAC shows high energy density and power density of 79.4 Wh/kg and 5.1 kW/kg, respectively, and impressive cyclic stability with 94.6 % after 5000 charge/discharge processes. More amazing, the soft-packaged supercapacitor presents stable electrochemical behaviors at multiple folding states and low pressure. This research may provide a completely new avenue for high-performance supercapacitor, even other application, such as secondary batteries, fuel cell, catalysis and purification system.

2. Experimental Section The Synthesis of 3DPAC and trGO: The 3DPAC was prepared by using wood dust as carbon sources and P123 as soft template via hydrothermal and carbonized treatment. Typically, wood dust (0.5 g) and P123 (0.2 g) were mixed in deionized water (80 mL) under magnetic stirring for 20 min. The formed dispersed solution were transferred to a Teflon-lined autoclave (100 ml) and heated at 180 °C for 12 h. Then, the intermediate product was washed by plenty of ethanol and water to obtain the precursor, which was subsequently pyrolyzed with KOH (the ratio of KOH and precursor was 4) as active agent under nitrogen atmosphere. The end product was washed with HCl solution and water to gain the 3DPAC. The synthesis of different 3DPAC was under different carbonization temperatures. In purpose of comparison, the trGO was prepared via thermally treating using graphene oxide from Modified Hummers’ method through the same process of 3DPAC. Materials characterization: The morphological characteristics were investigated by Scanning electron microscopy (SEM,


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SUPRA 55ZEISS, Germany) and Transimission electron microscopy (TEM, TECANI G2 F20 at 200 keV). The crystalline structure was probed on an X-Ray diffractometer (Ultima III X-ray diffractometer) using CuKα radiation in the 2θ range of 10 to 80°. Raman spectroscopy pattern was recorded with Renishaw Invia in the wavenumber from 400 to 4000 cm-1. Nitrogen sorption isotherms and aperture distribution curves were measured using a NOVA 2000e surface area and pore size analyzer at 77 K. The elemental composition was probed on an ESCALAB 250 X-ray photoelectron spectroscope (XPS). The electrolyte infiltration observations were performed with a contact angle meter. Electrochemical Evaluations: Electrodes used for electrochemical measurement were prepared by means of mixing active materials, conductive agent and binder with a mass of 80:12:8 in 1-Methyl-2-pyrrolidinone. The formed slurry was subsequently scraped coating onto the carbon nanotubes film current collector (prepared in laboratory) and dried at 100 °C for 24 h. the massing loading of active materials is ~5 mg/cm2. In three-electrode system, the electrochemical tests were performed in 6 M KOH aqueous electrolyte with Hg/HgO and platinum as reference electrode and counter electrode, respectively. In two-electrode system, symmetric supercapacitors were assembled employing the same electrode (loading mas 5 mg/cm2) with 1 mol/L Et4NBF4/AN organic electrolyte and glass fibrous as separator. The potential window of cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) based on three-electrode frame is ranged from -1.0 to 0 V. While the voltage window in two-electrode cell is arranged from 0 to 2.7 V. The electrochemical impedance spectroscopy (EIS) was carried out over the frequency range of 10-2-105 Hz a at open circuit potential with an amplitude of 10 mV. The gravimetric specific capacitance (Cg, F/g) in three-electrode or two-electrode system was acquired from the discharge curves by means of the following equation:

where I (A) is discharge current density, Δt (s) is discharge time and ΔV (V) is potential window in the discharge curves, respectively, and m (g) is the loading mass of 3DPAC materials. The energy density (E, Wh/kg) and power density (P, W/kg) were calculated according to the following equations:



Theoretical Calculation: First-principles electronic structure calculations were implemented based on the generalized gradient approximation (GGA) in the Perdew-Burke-Ernzerhof form. The interactions between ions and electrons were modeled by the projector-augmented wave method with a cutoﬀ energy of 600 eV. Uniform G-centered k-points meshes with a resolution of 2π*0.03 Å-1 and Methfessel-Paxton electronic smearing were utilized for the integration in the Brillouin zone. For geometric structure optimization, the vdW-D2 method of Grimme for van der Waals correction was adopted. These settings guarantee convergence of the total energies to within 1 meV per atom. Structure relaxation proceeded until all forces on atoms were less than 1 meV Å -1 and the total stress tensor was within 0.01 GPa of the target value.

3. Results and Discussion The overall procedure of fabricating the 3DPAC is schematically illustrated in Figure 1a. The pretreated wood dust firstly underwent hydrothermal reaction and followed carbonization treating to gain the objective. The original wood dust presented lamellar structure and the surface was flat and smooth. After the hydrothermal process, the lamellar structure separated a certain to sheet and the surface became rough (Figure S1, Supporting information). While without the addition of P123, the obtained 3DPAC only present macropore (Figure S2, Supporting information). Typically, the carbon nanosheets could evolve to generate with the carbonizing temperature increasing and the interpenetrating network structure could keep integrity at appropriate temperature (900°C) as shown in Figure S3 (Supporting Information). By contrast, the production prepared at low 800°C was block, which would result in small surface area. From the high temperature (1000°C), the obtained production was tattered without integrity network structure. It's also non-beneficial for electrolyte storage. The evolution of the structure for 3DPAC was detected by XRD, Raman spectroscopy and XPS. The as-synthesized 3DPAC prepared from 900 °C exhibits amorphous form with carbon nanosheet (Figure S4a and b), high specific surface area with rational pore size distribution (Figure S5a and b) and is rich with N and O doping


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(Figure S6, Supporting information). This unique structure endow 3DPAC electrode with excellent electrochemical performances (Figure S7 and 8, supporting informantion). The multistage pore structure characteristics of 3DPAC were further confirmed by TEM images. 3DPAC possess a macroporous features (Figure 1e), which consists of interconnected carbon nanosheet units with disordered structure (Figure 1f and g,), which is similar to the trGO (Figure S9a and b, Supporting information). However, compared with trGO, the 3DPAC displays hierarchical pores with microporous and macroporous with the exception of mesoporous (Figure S10, Supporting information). The electron diffraction pattern also displays that carbon nanosheets were in an amorphous state (Figure 1g). Such hierarchical open structure of 3DPAC can benefit to the storage and infiltration of electrolyte into the overall electrode materials and accelerating the electrolyte diffusion under folding and low-pressure condition.

a

c

b

d

5 μm

f

e

500 nm

100 nm

500 nm

g

5 nm

50 nm

Figure 1 (a) Schematic illustration of the fabrication process of 3DPAC; (b-d) SEM images of 3DPAC; (e-g) TEM images of 3DPAC



The structural features of 3DPAC and trGO were further confirmed through XRD pattern and Raman spectroscopy. As shown in Figure 2a, both XRD patterns of these two samples exhibit two bread diffraction peak at around 25° and 43°, corresponding to the (002) and (100) lattice face in amorphous carbon structure.[42] The diffraction peaks of the (002) face are at 25.6° and 25.1°, respectively. By contrast, the (002) peak of 3DPAC skews to a lower diffraction angle, delivering that the interplanar crystal spacing (d002) increases and the structure is more disordered,[43] which accord with the result of TEM. The d002 of 3DPAC is counted to be 0.419 nm, which is larger than that of trGO (0.395 nm). Figure 2b shows the Raman spectra of 3DPAC and trGO, presenting two obvious characteristic peaks at 1598 cm−1 and 1345 cm−1 of the G-band and the D-band peak, respectively. The G-band is ascribed to the graphitic structure, while the D-band is identified as the defect-induced structure,.[44] The intensity ratios of D-band to G-band peak (ID/IG) are counted to be 1.21 and 0.91 for 3DPAC and trGO, respectively, which further indicating a higher defective degree of 3DPAC. The increased half width at half maximum (HWHM) of G-band and D-band for 3DPAC also manifests a disordered structure.[45] The peak arising around 2690 cm−1 (2D) indicates the lamellar structure of 3DPAC. All these results are the mutual consistency, demonstrating the formation of graphitic carbon during carbonizing.

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390

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Binding Energy (eV)

410

415

520

525

530

535

Binding Energy (eV)

540

545

Figure 2 (a) XRD patterns, (b) Raman spectra and (c) BET of trGO and 3DPAC; (d) XPS spectra of 3DPAC; (e) high-resolution spectrum of N1s; (f) high-resolution spectrum of O1s

The porous structures of obtained materials were characterized by the nitrogen


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adsorption-desorption isotherms. Generally, the growth spurt at both lower pressure (P/P0< 0.1) and higher pressure (P/P0> 0.9) manifest the existence of luxuriant micropores and macropores, respectively.[46] The hysteresis of desorption located between 0.4 and 0.9 indicates the existing of mesopores.[47] As exhibited in Figure 2c, 3DPAC delivered a porous structure consisting of multi-size pore stretching over nanometer to submicron. The main structural parameters of 3DPAC and trGO acquired from the BET tests are summarized in Table S1 (Supporting information). 3DPAC reveals a high specific surface area of 2034 m2 g−1, which is significantly larger over the trGO (1628 m2 g−1). The increasing area should be attributed to the 3D network structure with micropores, mesopores and macropores (Table S1, supporting information). The pore size of 3DPAC is 4.09 nm, which is conducive to the storage and penetration of electrolyte. The XPS survey spectrum of 3DPAC expresses strong oxygen and nitrogen signal expect for carbon (Figure 2d). These heteroatoms are believed to be originated from the wood dust and no additional nitrogen and oxygen sources are required. The amount of N and O were 6.1 % and 7.9 %, respectively (Table S1, supporting information). High-resolution spectrum of N 1s (Figure 2e) deeply states that the valence states of nitrogen are mainly pyridinic nitrogen (N-6, 398.3 eV) and quaternary nitrogen (N-Q, 402.6 eV).[48-50] The doping of nitrogen has been verified to be the benefit of electron transmission in carbon materials.[51] In particular, N-6 atoms can supply pseudocapacitance and thus is capable of elevating the whole capacitance of 3DPAC, while N-Q atoms are the electron donors, which accelerates electron transfer. The O 1s peak (Figure 2f) can be decomposed into three peaks located at 531.2 eV, 532.4 eV and 533.4 eV, which are corresponding

to

the

binding

energy

of

C=O,

HC-O

and

C-O-C,

respectively.

Oxygen-functionalities have been demonstrated that can improve wettability of carbon nanomaterials and ease electrolyte diffusion into porous structure. Similarly, the addition of P123 is the doping of heteroatoms and the regulation of pore structure (Table S1, supporting information).



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4s

b

Figure 3 Comparison of the electrolyte infiltration between (a) 3DPAC and (b) trGO at different times

Incorporation of heteroatoms into carbon skeleton could regulate its electron-donor characters for well-pleasing electrical and chemical performance. Moreover, the doping of heteroatoms could increase the wettability between carbon materials and electrolyte, and decrease interfacial charge transfer resistance. The electrical conductivity of 3DPAC was tested to a value of 10.4 S/cm, superior to that of trGO (6.5 S/cm, Table S1, Supporting Information). Then, we use contact angle test to investigate the wettability between the as-prepared 3DPAC and electrolyte. As shown in Figure 3, the electrolyte drop (Et4NBF4/PC organic electrolyte) can still be clearly discerned remained on the trGO surface even after 4 s, while 3DPAC accomplishes an almost complete electrolyte infiltration within a shorter time of 2 s. These phenomenons strongly illustrate the much faster electrolyte penetration for 3DPAC, which could be ascribed to its three-dimensional network porous structure and stronger surface polarity arising from the abundant N and O element doping. All these structural features strongly support the obtained 3DPAC with faster diffusion of electrolyte ions and more penetrative and adsorptive active area, then leading to more excellent electrochemical performances.


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Figure 4 (a) Determination of the slope (b) for the logarithm of peak current versus logarithm of scan rate for trGO and 3DPAC; (b) Rate performance of trGO and 3DPAC from 1 A/g to 50 A/g; (c) EIS, (d) bode plots of phase angle vs frequency and (e) the imaginary capacitance Cʺ(ω) for trGO and 3DPAC; the inset shows the equivalent circuit; (f) Schematic diagram illustrating the transmission of electrons and diffusion of electrolyte ions at the surface of 3DPAC.

We first compared the electrochemical performance between 3DPAC and trGO in three-electrode system. To illuminate the classy charge-transfer kinetics, a comparative analysis of 3DPAC with trGO of peak current corresponding to the scan rate was implemented (Figure 4a). Assuming power-law dependence of the current, i, on scan rate, v: ip = avb The b value was equal to the slope of a straight line fitting from log i versus log v. Therefore, the b-value responds significant signal on the charge-transfer kinetics: b = 1 is characteristic for capacitive storage, while b = 0.5 indicates diffusion-limited processes.[52-53] Herein for the obtained 3DPAC, b approached 1 even when the scan rate up to 5 V/s, which reflected the ideal capacitive characteristic with fast electron conduction and high ion diffusion rate. 3DPAC exhibited a specific capacitance of 421 F/g at 1 A/g and 315 F/g at 50 A/g (Figure 4b). The rate capability was calculated to 80 %, which is better than that of trGO (69 %). EIS data were collected to deeply probe the ion transport properties. As shown in Figure 4c, 3DPAC exhibits a



relatively larger slope vertical line than that of rGO at low frequencies, manifesting a lower ion diffusion impedance. When at high frequencies, 3DPAC expresses an unconspicuous semicircle, implying small charge-transfer impedance. The Warburg curve in shorter 45° region was also observed, which demonstrating more effortless electrolyte diffusion into 3DPAC. The high-efficiency electronic/ionic transmissions are related to the network structure characteristics of 3DPAC. The Nyquist plots could be equivalent to an equivalent circuit (attached in Figure 4c). Figure 4d points the phase angle of the 3DPAC approximated to -90° at low frequencie, revealing an idea capacitive characteristics, and it beforehand reached -45° at the specific frequency (f0) of 0.77 Hz, endowing with a corresponding time (τ0) of 1.3 s. The τ0 of 3DPAC was much shorter than that of trGO which was counted to 8.3 s, revealing that the incorporation of heteroatoms doping had a positive effect on the ion-transfer kinetics. Additionally, the imaginary capacitance Cʺ(ω) for 3DPAC and trGO experienced a maximal value at a lower f0, confirming a faster time constant (Figure 4e). These results could be expounded by the model as shown in Figure 4f. The 3D network porous structure is to the benefit of electronic conduction and ionic diffusion. b

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Figure 5 (a) CV curves and (b) GCD curves of symmetric supercapacitor based 3DPAC in1 mol/L Et4NBF4/PC; (c) comparison of rate capability for 3DPAC and trGO from 1 to 32 A/g; (d) the Ragone plots of the 3DPC based on symmetric supercapacitor and comparison with previously reported carbon based symmetric supercapacitors; (e) the cycling performance of supercapacitor for 5000 cycles at 8 A/g, The left and right insets exhibit the GCD curves of the first five laps and last five cycles


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To explore the application of 3DPAC for supercapacitor active materials, a symmetric supercapacitor device with organic electrolyte was fabricated for the evaluating of electrochemical performance. As shown in Figure 5a, CVs tests of supercapacitor device were carried out in different scan rates and all the curves maintain a rectangular shape within a wide range of scan rates, even scan rate up to 500 mV/s, indicating that the device shows an representative and excellent electrochemical double-layer capacitance behavior and outstanding rate capability. The linear characteristic of charge/discharge curves at different current densities (Figure 5b) also reveals the EDLC behavior. The calculated specific capacitance is up to 78.5 F/g when the current density is 1 A/g, With the current density increasing to 32 A/g, the specific capacitance retains 83 % of initial value, all of which are better than that of trGO showed in Figure 5c. The energy density of obtained devices could realize a high valve of 79.4 Wh/kg at 1 A/g, which is higher than that of carbon based supercapacitors reported previously (Figure 5d and Table S2, Supporting Information).[37

54-61]

Meanwhile the power density could reach 5.1 kW/kg.

Furthermore, the cycling performance of device (Figure 5e) was measured and reveals 94.6 % of the primary capacitance preserved after 5 000 cycles. The GCD carves of last five cycles basically keep the same with the first five cycles, which demonstrating the excellent electrochemical stability of prepared supercapacitor. All in all, the outstanding electrochemical performances of device verify that the 3DPAC has good application value in supercapacitors.



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Figure 6 (a-d) Photographs of fan leaf lit by soft-packaged supercapacitor at different folding times; (e) CV curves, (f) GCD curves and (g) EIS spectra for soft-packaged supercapacitor based 3DPAC/CMF electrode at different folding angles; (h) Photographs of supercapacitor in low pressure; (i) CV curves and (j) cyclic performances of supercapacitor at different pressure.

We further investigated the resultant supercapacitor applying in some complex environments. As shown in Figure 6a-d, the soft-packaged supercapacitor powered a fan leaf with varied folding. The supercapacitor could proper functioning when subjected to three-time folding, at this moment the area of deice was shrunk with ~8 times. After reverting to the original, the device still worked well. The detailed electrochemical stability was tested by CV, GCD and EIS. There is almost no distinct excursion at low potential and only small deviation could be observed at high potential in CV curves (Figure 6e), the GCD curves also have the same characteristic with no damping (Figure 6f). The device with three-time folding showed brilliant rate capability (Figure S11, Supporting Information). Furthermore, the EIS of the device under different folding times also display similar behaviors in the full frequency (Figure 6g). The high frequency portion declares fast ion diffusion at the electrode/electrolyte interface and the x-intercept of the curve is connected with the interior contact resistance of whole system. The slope of spectrum line in low frequency


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district is the characteristic of ion diffusion and the representative of capacitance characteristics. Therefore, the folding strains almost have no remarkable influence on the ion diffusion and interior resistance, and the supercapacitor exhibits a nearly unchanged property even when the state reached to three-time folding (Figure S12, Supporting Information). This demonstrates its potential application as an efficient energy storage device for flexible and foldable electronic equipment. In addition, the supercapacitor was placed at low pressure (Figure 6h). Although the device expands, the device still show up excellent electrochemical stability, which was proved by the similar shape of CV curves at 500 mV/s (Figure 6i) and the GCD curves at 4 A/g (Figure 6j). When cycling the supercapacitor for 500 laps under low pressure, the capacitance retention is similar compared with ordinary pressure (Figure 6j and Movie S1, Supporting information). The considerable environmental suitability of this supercapacitor is attributed to the following points: (1) the porous carbon nanosheets could bear the outside force and maintain the integrity of three-dimensional network structure;[62-64] (2) the three-dimensional network structure endow 3DPAC with high capacity of storing electrolyte, even with exoteric force, the electrolyte could be stabilize in 3DPAC; (3) the carbon nanotubes film current collectors exhibit excellent flexible characteristic and the formed electrodes possess stable structure.

a

b

c

d

e

f

Figure 7 Graphical illustrations of the molecular structures of (a) 3DPAC, and Et4N+ adsorbed at (b) N-6, (c) N-5, (d) N-6(d), (e) -OH and (f) -O- sites, respectively.

To get insight into the good wettability between 3DPAC and electrolyte, the adsorption energy of Et4N+ on the N and O doping sites was simulated by means of density functional theory



(DFT). As shown in Figure 7a, a two layer carbon structure of 3DPAC with interlayer spacing of 0.419 nm is modeling, where N and O exist in the form of N-6. N-5, N-6(d), -O- and -OH respectively (Figure 7b-f). For the sake of evaluating the change of adsorption energy before and after NH4+ adsorption, the energy (EdG) is defined as the following Equation: Edg (ΔG)=E (Total)-E (Layer)-E (Et4N+) A positive EdG indicates an endothermic process and the Et4N+ adsorbing is unstable, while a negative EdG suggests an exothermic process and the adsorbing state is stable.[65] It is found that the EdG at the N and O doping sites are negative (Table S3), which manifests that electrolyte ions are adsorbed stably. This is accounted by that N and O doping are helpful to promote the adsorption ability and elevate the capacity. By contrast, rGO with an interlayer spacing of 0.391 nm was shown a positive EdG on the intact surface, suggesting that the adsorption is not easy and stable with respect to the bulk carbon layer. This consequence echoes well with the superior electrochemical properties of 3DPAC compared with rGO. Therefore, we can conclude that the obtained 3DPAC with O and N doping is expedient to the wettability of electrolyte and then perfect the electrochemical performance.

4. Conclusions In summary, a three-dimensional porous carbon nanosheets with N and O doping was prepared by a facile method combing hydrothermal method and carbonized treatment. Compared with trGO, the 3DPAC show plentiful porous structure and abundant element doping. This not only addresses the easy penetration and absorption of electrolyte ions, but also facilitates the rapid conduction of electrons. And then the supercapacitor based on 3DPAC exhibits high energy density and power density, outstanding cycling performance and inspiring environmental suitability (folding state and low pressure). Importantly, the preparation of 3DPAC was selected the abundant biomass waste wood dust as sources and required only the easy-to-use hydrothermal and carbonized treatment, both of which are highly scalable to reach the need for industrial manufacture. Therefore, the present 3DPAC may provide a completely new avenue for high-performance supercapacitor, even other application, such as batteries, fuel cell, catalysis and purification system.

Supporting Information


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SEM images; XRD patterns; Raman spectra; nitrogen adsorption–desorption isotherms; pore size distribution; Chemical composition; CV; GCD curves; rate capability and EIS of 3DPAC prepared at different tempretures. SEM and TEM images of trGO. Comparison of pore size distribution for trGO and 3DPAC. Comparison of electrochemical properties for 3DPAC with related materials. The electrochemical properties of flexible supercapacitors based on 3DPAC. And the adsorbing energy.

Acknowledgments This research was financially sponsored by the Project of Education Department of Jiangxi Province (Grant No. GJJ160649) and the Doctoral startup fund of Jiangxi University of Science and Technology (Grant No. 3401223242).

Reference [1] Zhong, C.; Deng, Y. D.; Hu, W. B.; Qiao, J. L.; Zhang, L.; Zhang, J. J., A Review of Electrolyte Materials and Compositions for Electrochemical Supercapacitors. Chem. Soc. Rev. 2015, 44, 7484-7539. [2] Tie, S. F.; Tan, C. W., A Review of Energy Sources and Energy Management System in Electric Vehicles. Renew. Sust. Energ. Rev. 2013, 20, 82-102. [3] Zhou, Z. B.; Benbouzid, M.; Charpentier, J. F.; Scuiller, F.; Tang, T. H., A Review of Energy Storage Technologies for Marine Current Energy Systems. Renew. Sust. Energ. Rev. 2013, 18, 390-400. [4] Simon, P.; Gogotsi, Y., Materials for Electrochemical Capacitors. Nat. Mater. 2008, 7, 845-854. [5] Beguin, F.; Presser, V.; Balducci, A.; Frackowiak, E., Carbons and Electrolytes for Advanced Supercapacitors. Adv. Mater. 2014, 26, 2219-2251. [6] Liu, X. B.; Shang, P. B.; Zhang, Y. B.; Wang, X. L.; Fan, Z. M.; Wang, B. X.; Zheng, Y. Y., Three-Dimensional and Stable Polyaniline-Grafted Graphene Hybrid Materials for Supercapacitor Electrodes. J. Mater. Chem. A 2014, 2, 15273-15278. [7] Wu, Z. S.; Parvez, K.; Feng, X. L.; Mullen, K., Graphene-based in-Plane Micro-Supercapacitors with High Power and Energy Densities. Nat. Commun. 2013, 4. 2487. [8] Hou, L. R., Chen, Zh. Y., Zhao, Zh. W., Sun,X., Zhang, J. Y. and Yuan, Ch. Zh., Universal FeCl3-Activating Strategy for Green and Scalable Fabrication of Sustainable Biomass-Derived Hierarchical Porous Nitrogen-Doped Carbons for Electrochemical Supercapacitors. ACS Appl. Energy Mater., 2019, 2, 548–557. [9] Li, X.; Wei, B. Q., Supercapacitors based on Nanostructured Carbon. Nano Energy 2013, 2, 159-173. [10] Wang, G. P.; Zhang, L.; Zhang, J. J., A Review of Electrode Materials for Electrochemical Supercapacitors. Chem. Soc. Rev. 2012, 41, 797-828. [11] Simon, P.; Gogotsi, Y.; Dunn, B., Where Do Batteries End and Supercapacitors Begin? Science



2014, 343, 1210-1211. [12] Black J M and Andreas H A. Pore Shape Affects Spontaneous Charge Redistribution in Small Pores. J Phys Chem C, 2010, 114, 12030-12038. [13] Ervin M H. Etching Holes in Graphene Supercapacitor Electrodes for Faster Performance. Nanotechnology, 2015, 26, 234003. [14] Zhang, F.; Liu, T. Y.; Li, M. Y.; Yu, M. H.; Luo, Y.; Tong, Y. X.; Li, Y.. Multiscale Pore Network Boosts Capacitance of Carbon Electrodes for Ultrafast Charging. Nano Lett, 2017, 17, 3097-3104. [15] Simon, P.; Gogotsi, Y., Capacitive Energy Storage in Nanostructured Carbon-Electrolyte Systems. ACC Chem. Res. 2013, 46, 1094-1103. [16] Yao, L.; Wu, Q.; Zhang, P. X.; Zhang, J. M.; Wang, D. R.; Li, Y. L.; Ren, X. Z.; Mi, H. W.; Deng, L. B.; Zheng, Z. J., Scalable 2D Hierarchical Porous Carbon Nanosheets for Flexible Supercapacitors with Ultrahigh Energy Density. Adv. Mater. 2018, 30, 1706054. [17] Nardecchia, S.; Carriazo, D.; Ferrer, M. L.; Gutierrez, M. C.; del Monte, F., Three Dimensional Macroporous Architectures and Aerogels Built of Carbon Nanotubes and/or Graphene: Synthesis and Applications. Chem. Soc. Rev. 2013, 42, 794-830. [18] Yu, Z. N.; Tetard, L.; Zhai, L.; Thomas, J., Supercapacitor Electrode Materials: Nanostructures from 0 to 3 Dimensions. Energ. Environ. Sci. 2015, 8, 702-730. [19] Wu, Z. S.; Winter, A.; Chen, L.; Sun, Y.; Turchanin, A.; Feng, X. L.; Mullen, K., Three-Dimensional Nitrogen and Boron Co-Doped Graphene for High-Performance All-Solid-State Supercapacitors. Adv. Mater. 2012, 24, 5130-5135. [20] Liu, X. B.; Wu, Z. P.; Yin, Y. H., Highly Nitrogen-Doped Graphene Anchored with Co3O4 Nanoparticles as Supercapacitor Electrode with Enhanced Electrochemical Performance. Synthetic Met. 2017, 223, 145-152. [21] Wei, X. J.; Jiang, X. Q.; Wei, J. S.; Gao, S. Y., Functional Groups and Pore Size Distribution Do Matter to Hierarchically Porous Carbons as High-Rate-Performance Supercapacitors. Chem. Mater. 2016, 28, 445-458. [22] Hao, L.; Ning, J.; Luo, B.; Wang, B.; Zhang, Y. B.; Tang, Z. H.; Yang, J. H.; Thomas, A.; Zhi, L. J., Structural Evolution of 2D Microporous Covalent Triazine-based Framework Toward the Study of High-Performance Supercapacitors. J. Am. Chem. Soc. 2015, 137, 219-225. [23] Zhang, L.; Yang, X.; Zhang, F.; Long, G. K.; Zhang, T. F.; Leng, K.; Zhang, Y. W.; Huang, Y.; Ma, Y. F.; Zhang, M. T.; Chen, Y. S., Controlling the Effective Surface Area and Pore Size Distribution of sp2 Carbon Materials and Their Impact on the Capacitance Performance of These Materials. J. Am. Chem. Soc. 2013, 135, 5921-5929. [24] Sentorun-Shalaby, C.; Ucak-Astarlioglu, M. G.; Artok, L.; Sarici, C., Preparation and Characterization of Activated Carbons by One-Step Steam Pyrolysis/Activation from Apricot Stones. Micropor. Mesopor. Mater. 2006, 88, 126-134. [25] Guo, J.; Luo, Y.; Lua, A. C.; Chi, R. A.; Chen, Y. L.; Bao, X. T.; Xiang, S. X., Adsorption of Hydrogen Sulphide (H2S) by Activated Carbons Derived from Oil-Palm Shell. Carbon 2007, 45, 330-336. [26] Elmouwahidi, A.; Zapata-Benabithe, Z.; Carrasco-Marin, F.; Moreno-Castilla, C., Activated Carbons from KOH-Activation of Argan (Argania Spinosa) Seed Shells as Supercapacitor Electrodes. Bioresource Technol. 2012, 111, 185-190. [27] Wickramaratne, N. P.; Xu, J. T.; Wang, M.; Zhu, L.; Dai, L. M.; Jaroniec, M., Nitrogen Enriched


Page 18 of 22

Page 19 of 22 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Porous Carbon Spheres: Attractive Materials for Supercapacitor Electrodes and CO2 Adsorption. Chem. Mater. 2014, 26, 2820-2828. [28] Zhou, L.; Cao, H.; Zhu, S. Q.; Hou, L. R.; Yuan, C. Z., Hierarchical Micro-/Mesoporous N- and O-enriched Carbon Derived from Disposable Cashmere: A Competitive Cost-Effective Material for High-Performance Electrochemical Capacitors. Green Chem 2015, 17, 2373-2382. [29] Niu, J.; Shao, R.; Liang, J. J.; Dou, M. L.; Li, Z. L.; Huang, Y. Q.; Wang, F., Biomass-Derived Mesopore-Dominant Porous Carbons with Large Specific Surface Area and High Defect Density as High Performance Electrode Materials for Li-Ion Batteries and Supercapacitors. Nano Energy 2017, 36, 322-330. [30] Zhao, L.; Fan, L. Z.; Zhou, M. Q.; Guan, H.; Qiao, S. Y.; Antonietti, M.; Titirici, M. M., Nitrogen-Containing Hydrothermal Carbons with Superior Performance in Supercapacitors. Adv. Mater. 2010, 22, 5202. [31] Wei, L.; Sevilla, M.; Fuertes, A. B.; Mokaya, R.; Yushin, G., Hydrothermal Carbonization of Abundant Renewable Natural Organic Chemicals for High-Performance Supercapacitor Electrodes. Adv. Energy Mater. 2011, 1, 356-361. [32] Feng, S. S.; Li, W.; Wang, J. X.; Song, Y. F.; Elzatahry, A. A.; Xia, Y. Y.; Zhao, D. Y., Hydrothermal Synthesis of Ordered Mesoporous Carbons from a Biomass-Derived Precursor for Electrochemical Capacitors. Nanoscale 2014, 6, 14657-14661. [33] Salinas-Torres, D.; Lozano-Castello, D.; Titirici, M. M.; Zhao, L.; Yu, L. H.; Morallon, E.; Cazorla-Amoros, D., Electrochemical Behaviour of Activated Carbons Obtained via Hydrothermal Carbonization. J. Mater. Chem. A 2015, 3, 15558-15567. [34] Lin, X. X.; Tan, B.; Peng, L.; Wu, Z. F.; Xie, Z. L., Ionothermal Synthesis of Microporous and Mesoporous Carbon Aerogels from Fructose as Electrode Materials for Supercapacitors. J. Mater. Chem. A 2016, 4, 4497-4505. [35] Wang, D. W.; Liu, S. J.; Jiao, L.; Fang, G. L., A Smart Bottom-Up Strategy for the Fabrication of Porous Carbon Nanosheets Containing rGO for High-Rate Supercapacitors in Organic Electrolyte. Electrochim. Acta, 2017, 252, 109-118. [36] Guo, N. N.; Li, M.; Wang, Y.; Sun, X. K.; Wang, F.; Yang, R., Soybean Root-Derived Hierarchical Porous Carbon as Electrode Material for High-Performance Supercapacitors in Ionic Liquids. ACS Appl. Mater. Inter. 2016, 8, 33626-33634. [37] Zhang, W. L.; Lin, H. B.; Lin, Z. Q.; Yin, J.; Lu, H. Y.; Liu, D. C.; Zhao, M. Z., 3D Hierarchical Porous Carbon for Supercapacitors Prepared from Lignin through a Facile Template-Free Method. ChemSusChem 2015, 8, 2114-2122. [38] Liu, B.; Liu, Y. J.; Chen, H. B.; Yang, M.; Li, H. M., Oxygen and Nitrogen Co-doped Porous Carbon Nanosheets Derived from Perilla Frutescens for High Volumetric Performance Supercapacitors. J. Power Sources 2017, 341, 309-317. [39] Yao, Y.; Wu, F., Naturally Derived Nanostructured Materials from Biomass for Rechargeable Lithium/Sodium Batteries. Nano Energy 2015, 17, 91-103. [40] Dutta, S.; Bhaumik, A.; Wu, K. C. W., Hierarchically Porous Carbon Derived from Polymers and Biomass: Effect of Interconnected Pores on Energy Applications. Energ. Environ. Sci. 2014, 7, 3574-3592. [41] Long, W. Y.; Fang, B. Z.; Ignaszak, A.; Wu, Z. Z.; Wang, Y. J.; Wilkinson, D., Biomass-derived Nanostructured Carbons and Their Composites as Anode Materials for Lithium Ion Batteries. Chem. Soc. Rev. 2017, 46, 7176-7190.



[42] Fan, L.; Liu, Q.; Chen, S. H.; Xu, Z.; Lu, B. G., Soft Carbon as Anode for High-Performance Sodium-Based Dual Ion Full Battery. Adv. Energy Mater. 2017, 7, 1602778. [43] Wang, D. W.; Liu, S. J.; Jiao, L.; Fang, G. L.; Geng, G. H.; Ma, J. F., Unconventional Mesopore Carbon Nanomesh Prepared through Explosion–Assisted Activation Approach: A Robust Electrode Material for Ultrafast Organic Electrolyte Supercapacitors. Carbon, 2017, 119, 30-39. [44] Ferrari, A. C.; Meyer, J. C.; Scardaci, V.; Casiraghi, C.; Lazzeri, M.; Mauri, F.; Piscanec, S.; Jiang, D.; Novoselov, K. S.; Roth, S.; Geim, A. K., Raman Spectrum of Graphene and Graphene Layers. Phys. Rev. Lett. 2006, 97, 187401. [45] Dresselhaus, M. S.; Jorio, A.; Hofmann, M.; Dresselhaus, G.; Saito, R., Perspectives on Carbon Nanotubes and Graphene Raman Spectroscopy. Nano Lett. 2010, 10, 751-758. [46] Zhao, J.; Lai, H. W.; Lyu, Z. Y.; Jiang, Y. F.; Xie, K.; Wang, X. Z.; Wu, Q.; Yang, L. J.; Jin, Z.; Ma, Y. W.; Liu, J.; Hu, Z., Hydrophilic Hierarchical Nitrogen-Doped Carbon Nanocages for Ultrahigh Supercapacitive Performance. Adv. Mater. 2015, 27, 3541-3545. [47] Wang, G. M.; Wang, H. Y.; Lu, X. H.; Ling, Y. C.; Yu, M. H.; Zhai, T.; Tong, Y. X.; Li, Y., Solid-State Supercapacitor based on Activated Carbon Cloths Exhibits Excellent Rate Capability. Adv. Mater. 2014, 26, 2676-2682. [48] Yan J.; Wang Q.; Lin C. P.; Wei T.; Fan Z. J., Interconnected Frameworks with a Sandwiched Porous Carbon Layer/Graphene Hybrids for Supercapacitors with High Gravimetric and Volumetric Performances. Adv. Energy Mater. 2014, 4, 1400500. [49] Yi, Z. R.; Zhang, Z. Y.; Wang, S. A.; Shi, G. Q., Pyridinic Nitrogen-Rich Carbon Nanocapsules from a Bioinspired Polydopamine Derivative for Highly Efficient Electrocatalytic Oxygen Reduction. J. Mater. Chem. A 2017, 5, 519-523. [50] Lin, Y. C.; Teng, P. Y.; Yeh, C. H.; Koshino, M.; Chiu, P. W.; Suenaga, K., Structural and Chemical Dynamics of Pyridinic-Nitrogen Defects in Graphene. Nano Lett. 2015, 15, 7408-7413. [51] Wang, D. W.; Li, F.; Yin, L. C.; Lu, X.; Chen, Z. G.; Gentle, I. R.; Lu, G. Q.; Cheng, H. M., Nitrogen-Doped Carbon Monolith for Alkaline Supercapacitors and Understanding Nitrogen-Induced Redox Transitions. Chem-Eur. J. 2012, 18, 5345-5351. [52] Lukatskaya, M. R.; Kota, S.; Lin, Z. F.; Zhao, M. Q.; Shpigel, N.; Levi, M. D.; Halim, J.; Taberna, P. L.; Barsoum, M.; Simon, P.; Gogotsi, Y., Ultra-High-Rate Pseudocapacitive Energy Storage in Two-Dimensional Transition Metal Carbides. Nat. Energy 2017, 2. 17105. [53] Wang, H. W.; Zhu, C. R.; Chao, D. L.; Yan, Q. Y.; Fan, H. J., Nonaqueous Hybrid Lithium-Ion and Sodium-Ion capacitors. Adv. Mater. 2017, 29, 1702093. [54] Qian, W. J.; Sun, F. X.; Xu, Y. H.; Qiu, L. H.; Liu, C. H.; Wang, S. D.; Yan, F., Human Hair-Derived Carbon Flakes for Electrochemical Supercapacitors. Energ. Environ. Sci. 2014, 7, 379-386. [55] Liang, Q. H.; Ye, L.; Huang, Z. H.; Xu, Q.; Bai, Y.; Kang, F. Y.; Yang, Q. H., A Honeycomb-like Porous Carbon Derived from Pomelo Peel for Use in High-Performance Supercapacitors. Nanoscale 2014, 6, 13831-13837. [56] Raymundo-Pinero, E.; Cadek, M.; Beguin, F., Tuning Carbon Materials for Supercapacitors by Direct pyrolysis of Seaweeds. Adv. Funct. Mater. 2009, 19, 1032-1039. [57] Feng, H. B.; Hu, H.; Dong, H. W.; Xiao, Y.; Cai, Y. J.; Lei, B. F.; Liu, Y. L.; Zheng, M. T., Hierarchical Structured Carbon Derived from Bagasse Wastes: a Simple and Efficient Synthesis Route and Its Improved Electrochemical Properties for High-Performance Supercapacitors. J. Power Sources 2016, 302, 164-173.


Page 20 of 22

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[58] Zhang, C. Y.; Zhu, X. H.; Cao, M.; Li, M. L.; Li, N.; Lai, L. Q.; Zhu, J. L.; Wei, D. C., Hierarchical Porous Carbon Materials Derived from Sheep Manure for High-Capacity Supercapacitors. ChemSusChem 2016, 9, 932-937. [59] Niu, Q. Y.; Gao, K. Z.; Tang, Q. H.; Wang, L. Z.; Han, L. F.; Fang, H.; Zhang, Y.; Wang, S. W.; Wang, L. X., Large-Size Graphene-like Porous Carbon Nanosheets with Controllable N-Doped Surface Derived from Sugarcane Bagasse Pith/Chitosan for High Performance Supercapacitors. Carbon 2017, 123, 290-298. [60] Liu, Y. X.; Xiao, Z. C.; Liu, Y. C.; Fan, L. Z., Biowaste-Derived 3D Honeycomb-like Porous Carbon with Binary-Heteroatom Doping for High-Performance Flexible Solid-State Supercapacitors. J. Mater. Chem. A 2018, 6, 160-166. [61] Xie, L. J.; Sun, G. H.; Su, F. Y.; Guo, X. Q.; Kong, Q. Q.; Li, X. M.; Huang, X. H.; Wan, L.; Song, W.; Li, K. X.; Lv, C. X.; Chen, C. M., Hierarchical Porous Carbon Microtubes Derived from Willow Catkins for Supercapacitor Applications. J. Mater. Chem. A 2016, 4, 1637-1646. [62] Lin, R.; Taberna, P. L.; Chmiola, J.; Guay, D.; Gogotsi, Y.; Simon, P., Microelectrode Study of Pore Size, Ion Size, and Solvent Effects on the Charge/Discharge Behavior of Microporous Carbons for Electrical Double-Layer Capacitors. J. Electrochem. Soc. 2009, 156, A7-A12. [63] Pandolfo, A. G.; Hollenkamp, A. F., Carbon Properties and Their Role in Supercapacitors. J. Power Sources 2006, 157, 11-27. [64] Chen, Z. Y.; Sun, J. F.; Bao, R. Q.; Sun, X.; Zhang, J. Y.; Hou, L. R.; Yuan, C. Z., A General Eco-friendly Production of Bio-sources Derived Micro-/Mesoporous Carbons with Robust Supercapacitive Behaviors and Sodium-Ion Storage. ACS Sustain. Chem. Eng., 2019, 7, 779-789. [65] Chen, M.; Wang, W.; Liang, X.; Gong, S.; Liu, J.; Wang, Q.; Guo, S. J.; Yang, H., Sulfur/Oxygen Codoped Porous Hard Carbon Microspheres for High-Performance Potassium-Ion Batteries. Adv. Energy Mater. 2018, 8, 1800171.



Table of Content Title: Superb Electrolyte Penetration/Absorption of 3D Porous Carbon Nanosheets for Multifunctional Supercapacitor


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Absorption of Three-Dimensional

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