One-dimensional hierarchically porous carbon from biomass with high capacitance as supercapacitor materials

Accepted Manuscript One-dimensional hierarchically porous carbon from biomass with high capacitance as supercapacitor materials Chen Liang, Jinpeng Bao, Chunguang Li, He Huang, Cailing Chen, Yue Lou, Haiyan Lu, Haibo Lin, Zhan Shi, Shouhua Feng PII:

S1387-1811(17)30371-2

DOI:

10.1016/j.micromeso.2017.05.044

Reference:

MICMAT 8357

To appear in:

Microporous and Mesoporous Materials

Received Date: 28 March 2017 Revised Date:

19 May 2017

Accepted Date: 20 May 2017

Please cite this article as: C. Liang, J. Bao, C. Li, H. Huang, C. Chen, Y. Lou, H. Lu, H. Lin, Z. Shi, S. Feng, One-dimensional hierarchically porous carbon from biomass with high capacitance as supercapacitor materials, Microporous and Mesoporous Materials (2017), doi: 10.1016/ j.micromeso.2017.05.044. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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One-dimensional Hierarchically Porous Carbon from Biomass with High Capacitance as Supercapacitor Materials Chen Liang a, 1, Jinpeng Bao b, 1, Chunguang Li a, He Huang a, Cailing Chen a, Yue Lou a, Haiyan Lu b, *, Haibo Lin,b Zhan Shi a, **, and Shouhua Fenga a

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State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,

Changchun 130012, People’s Republic of China. b

College of Chemistry, Jilin University, Changchun 130012, People’s Republic of China.

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HIGHLIGHTS

Biomass-derived one-dimensional hierarchical pore carbon (1-DHPC) was synthesized.

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The specific structure is conducive to the diffusion of charges.

Good capacitance of 256.5 F g-1 and low equivalent series resistance of 0.16 Ω was obtained. Abstract

One-dimensional hierarchically porous carbon was prepared by carbonized and activated plant

materials.

Scanning

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metaplexis and exhibited large surface area and high performance as supercapacitor electrode electron

microscope,

transmission

electrode

microscope,

X-ray

spectroscopy, X-ray photoelectron spectroscopy, and Raman were used to characterize the

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microtopography and chemical composition of the materials as well as their transformation during the preparation process. With specific surface area (1394m2 g-1) and fine electrochemistry

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performance, the product exhibited a capacitance of 256.5 F g-1 at 5 mV s-1 and a very low

1

These authors have equally contributed.

*

Corresponding author.

**

Corresponding author. E-mail addressed: [email protected] (H. Lu), [email protected] (Z. Shi).

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equivalent series resistance of 0.16 Ω. The fine supercapacitor performance could be attributed to the hierarchically porous, large surface area and the specific ultralong tubular structure.

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Keywords: Biomass, hierarchical porous carbon, one-dimensional nanomaterial, supercapacitors

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1. Introduction

Portable energy storage devices are needed by an increasing number of devices such as wind

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turbines, mobile phones, laptops, unmanned aerial vehicles and the rapidly advancing electric vehicles, which will reduce our dependence on oil and contribute to the betterment of the environment.[1, 2] Supercapacitors play an important role in the development of electrical energy storage devices, because the materials fill in the gap between batteries and conventional

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capacitors, covering several orders of magnitude both in energy and power densities.[3, 4] With huge surface area, tiny gap between positive and negative and no electrochemical reaction during charge-discharge, supercapacitors exhibit superiority in electrochemistry, such as fast

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charge/discharge rate (10 s to 10 min charging can reach 95% of the rated capacity), long repeat service life (over 106 cycles),[5] large potential window, high energy transformation efficiency

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and low loss during the process (high current cycle efficiency ≥ 90%), high conductivity, large effective surface area and safety.[6] Supercapacitors can be classified into pseudocapacitors and electrical double-layer capacitors (EDLCs) based on their charge-storage mechanism. For the latter, electrolyte ions adsorb on large surface area conductive electrodes, in which the surface charge is separated at electrode/electrolyte interfaces.[7, 8] Much relevant work has been reported in recent years.

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Some biomass in nature can serve as good electrochemical materials after processing. For example, natural silk was activated and graphitized to form hierarchically porous nitrogen-doped carbon, exhibiting a capacitance of 242 F g-1 and density of 102Wh kg-1;[9] porous graphene-like

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nanosheets with a large surface area were prepared by cost-effective simultaneous activationgraphitization from waste coconut shell, which reached a specific capacitance of 268 F g-1;[10] murdannia simplex stalks were used as the appropriate carrier to load Co3O4 nanoparticles due to

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their hierarchically porous structure. The products maintained a high reversible capacity of 1215mAh g-1 as an anode material for lithium-ion batteries;[11] heteroatom doped porous carbon

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flakes were prepared via carbonization of Chinese human hair fibers and exhibited high charge storage capacity with a specific capacitance of 340 F g-1 in 6 M KOH at a current density of 1 A g-1 and good stability over 20 000 cycles for high-performance supercapacitor electrode materials;[12] a hierarchical lamellar porous material was prepared with fish scale using a

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natural template. The capacitance was 168 F g-1 at a current density of 0.05 A g-1 and remained at 130 F g-1 even at a high current density of 40 A g-1.[13] Engineering the micro-structure of carbon materials and their pore structures is thus vital for

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improving their performance by providing better electrolyte permeability, ion transport/

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diffusion, electron-transfer path and higher charge-induced ion-adsorbing surface area.[14-16] This is why mass work of carbon nanotube (CNT) and graphene used for electrochemistry were expanded when it was discovered.[17-20] Specific morphology materials have been prepared from different ways. Graphene-like nitrogen-doped carbon nanosheet has been constructed by using simultaneous carbonization and auto-activation followed by ultrasonic-assisted liquid exfoliation from layered shrimp shells.[21] Two-dimensional porous carbon sheet has been prepared by carbonization of organic alkali salts, namely in situ activation, used for

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electrochemical capacitors.[14] But less work about one-dimensional biomass materials used as electrochemical materials has been reported because most microstructures of the samples tend to

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be destroyed in the preparation process.[12, 14] After long-term evolution and selection, many biologies are born with ingenious structure. Plenty of outstanding achievements were inspired by observing and imitating the structure of

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biomass.[22-25] Metaplexis plants are vines that reach 8 m high, are rhizomatous and have underground woody organs that constitute a pattern, corolla white, sometimes with purplish

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stripes, tube short, lobes lanceolate, slightly longer than sepals, spreading reflexed at apex, and conspicuously pilose inside. This kind of plants is widespread across much of China, also Korea, Japan, and Russian Far East.[26] The plant is commonly used as traditional Chinese medicinal materials, but we found that the fibers in the seeds are a good raw material for electrochemistry. The fiber with one-dimensional structure is a good bridge for the electron transport and ion

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diffusion, and there has been much work preparing 1-D materials via complicated processes. Inspired by its morphology, we tried to treat the plant with some method to meet the requirement of electrode materials. We stripped out the fibers from the seeds, created a mass of micropores in

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the wall of the tube without destroying the morphology. The large surface area and specific one-

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dimension structure contribute to the good electrochemistry properties. The materials exhibit high capacitance of 265 F g-1 but very low equivalent series resistances (ESR) of 0.16 Ω in 6 M KOH.

2. Experimental

2.1 Synthesis of one-dimensional hierarchically porous carbon from metaplexis japonica

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Metaplexis japonica was shelled and removed from the seeds carefully. Filaments were collected and ultrasound in deionized water to clear the dust, dried at 100 oC overnight after that. The cleaned filaments were transferred into tube furnace and carbonized at 500 oC for 1 h with a

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heating rate of 5 oC min-1 in a N2 atmosphere to yield macropores in the wall of the tube. After natural cooling to room temperature, the carbonized filaments were heated at 100 oC for 2.5 h in solution with 5% NaOH to remove metal ions within the plant. The solution was filtrated after

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cooling, and the filaments were dried in oven. The sample was activated in 750 oC tube furnace and kept 1 h with the same heating rate of carbonization under a N2 atmosphere after being

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soaked in solution made of KOH (4 time of sample mass) 30 min with slight stirring and then dried. After cooling to room temperature, the sample was washed with boiling water to remove the excess KOH and dried in oven to obtain the final product.

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2.2 Characterization

The morphology of the products was examined using a JEOL JSM-6700F scanning electron microscope (SEM) at 5kV. Transmission electron microscopy (TEM) images and energy-

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dispersive spectrometer (EDS) are collected with a FEI Tecnai G2 S-Twin F20 TEM at 200kV. Thermogravimetric analysis (TGA) was performed with a NETZSCH STA 449C thermo-balance

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in nitrogen with a heating rate of 10 oC min-1 to 800 oC. X-ray photoelectron spectra (XPS) were obtained using an ESCALAB250 spectrometer (Thermo Electron Corporation) with an excitation source of Mg Kα radiation. Raman spectra were obtained with an INVIA from Renishaw. Nitrogen adsorption-desorption (77 K) analysis was carried out on a Micromeritics ASAP 2020 surface area and porosity analyser. X-ray diffraction (XRD) was conducted using a Rigaku D/MAX-2550 with Cu Kα radiation.

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2.3 Electrochemical test Electrochemical characterization was carried out on 2273 electrochemical workstation

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(Princeton Applied research) at room temperature. 80 wt% HPC was mixed with 10 wt% PTEF and 10 wt% carbon black. The viscous slurry was pressed onto a nickel form current collector at 15 Mpa. The prepared electrodes were dried in a vacuum oven. Each electrode contained 5.57

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mg sample. A Hg/HgO, a Pt wire and the above loaded nickel foam were used as the reference, counter and working electrodes, respectively. Cyclic voltammetry curves were measured in the

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potential range of -0.8 ~ 0.6 V vs. Hg/HgO from 5 to 50 mV S-1. An aqueous solution containing 6 M KOH was employed as the electrolyte. EIS was obtained in a frequency range of 0.1 Hz to 100 kHz at open circuit voltage with a scan rate of 5 mV. The following equation was used to calculate the specific capacitance:[27]

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C=

∆ ∆

I (A) refers to the discharge current, t (s) is the discharge time, (V) represents potential change

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during discharge process and m (g) refers to the mass of the sample in the working electrode.

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3. Results and discussion

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Fig. 1. Images of metaplexis japonica with naked eye (a) and TEM (b), SEM images of the materials after being carbonized with different magnification (c,d), and SEM images of materials

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after being activated with different magnification (e,f).

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Fig. 2. The simulation models of three characteristic states of the material representing the reaction process. As is shown in Fig. 1a, each filament of metaplexis japonica is a white fiber with naked eye, but

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a tube when observed with SEM or TEM, with regular circular hole in the central and smooth straight wall (Fig. 1b). The average inside and outside diameter is 23 µm and 27 µm respectively, while the average thickness of the wall is about 2 µm. After 500 oC carbonization under nitrogen,

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the sample turned to black fiber, while the wall of the tube shrinked to the centre and turned to two or more tubes, the average diameter of the tube being about 4 µm. But the sample

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maintained the structure of a straight tube with shrinking pore diameter and smooth compact wall. The wall of the tube is well protected without damage (Fig. 1c and d). After being activated in the 750 oC tube furnace with KOH, no obvious morphology change occurred to the sample according to the SEM images (Fig. 1e and f), but the sample was activated and a mass of micropores was produced in the wall of the tube, which could be proved by the data of nitrogen sorption in the later section of this article. Figure 2 illustrates a schematic diagram for the

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preparation of one-dimensional hierarchically porous carbon (1-D-HPC). The cleaned metaplexis

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japonica was carbonized and activated with KOH in N2.

Fig. 3. EDS and mapping of Cu, Fe, Ca, K and high angel annular dark field (HADDF) after carbonization.

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Elements form of the plants was detected by the following measurements. The EDS and

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mapping shown in Fig. 3 reveal the existence of metal elements in the metaplexis japonica, such as Ca, Cu, Fe and K. It should be noted that the content of Cu in the EDS and mapping might be misinformation because the copper net for sample supporting could contribute to both measurement. The existence of Nitrogen element in the material can enhance the surface wettability of carbon materials and induce pseudocapacity behaviour (Fig. S1).[28, 29] But the metallic elements are against electrochemistry, because they are instable in the charge/discharge process. The materials were washed after carbonization with 5% NaOH solution to remove the

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metallic elements, and then the solution was sent for ICP to analyze the components of the plant. The content of Ca, Cu, Fe and K is 5.468, 0.1618, 0.6941 and 0.9832 ppm, respectively (Table S1). The major ingredient of the white powder was CaCO3 according to the XRD of the material

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after being carbonized in air, which is consistent with the result of ICP (Fig. S2).

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Fig. 4. TG and DTG curve of metaplexis japonica under nitrogen. The TG curve matches well with the components of the sample (Fig. 4). The main components of the plants are cellulose, lignin, hemicellulose, and pectin. The decomposition temperature of

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cellulose is between 200 ~ 375 oC. The cellulose pyrolysed to dehydrated cellulose between 200

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~ 280 oC, and subsequently decomposed into a plethora of charcoal and gaseous products. When the temperature was up to 280 ~ 340 oC， the sample decomposed into a plethora of volatile substances such as tar.[30-34] Some oily product was observed on the wall of the tube furnace after carbonization. The sample transformed into aromatic structure when the temperature was over 400 oC, similar to the structure of graphite, which will be confirmed by the data of Raman and XPS.

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Fig. 5. C 1s XPS spectrum of material after being carbonized (a) and activated (b).

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More detailed analysis was carried out using XPS and Raman spectra (Fig. 5,6). The C 1s Spectrum for HPC presented in Figures 5 a and b can be deconvoluted into 4 major peaks, including C-C (284.7 eV), C-N (285.6 eV), C-O (286.7 eV) and C=O (288.1eV).[18, 21, 35, 36] 79.69% carbon-carbon bonds were calculated from the XPS-peak-differentiating analysis of the sample after activation, which is higher than the carbonized material (77.85%) (Table S2). Because the higher temperature lead to more graphitization.

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Fig. 6. Raman of the material after carbonization (a), activation (b) and their comparison(c).

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Raman curve matches well with the data of XPS. Raman spectra show two peaks at 1360 and 1585 cm-1 representing the D and G band respectively (Fig. 6a and b).[37] The G band is a

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characteristic feature of graphitic layers and corresponds to the tangential vibration of carbon atoms while the D band relates to disordered carbon or defective graphitic structures.[38] The proportion of D and G is 80 % and 20 % respectively in the material of carbonization, ID/IG =4; while the D and G proportion of the activation sample is 74 % and 26 % respectively, ID/IG =

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2.85. The difference is obvious in the comparison of the curves in Fig. 6c. The change indicates an increased graphitization degree with the reaction in the process of carbonization and activation because of the second calcine and higher temperature.

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The activation with KOH caused pores to form within the wall of the tube according to the

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following chemical reaction:[39]

6KOH + 2C → 2K + 3 → +

+2

+ →2

; ;

+2 →2 +3 +

→2 +

;

; .

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The carbonized material was mixed with the crushed KOH directly at the stage of exploration, but the specific morphology of the material caused insufficient contact. Considerable caking KOH was observed at the bottom of the sample, which is bound to the inhomogenous activation.

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So we immersed the carbonization material into the KOH solution to obtain uniform adhesion.

Fig. 7. Nitrogen sorption istherms (a) and pore size distribution (b) of carbonization and activation.

The nitrogen sorption isotherms and pore size distribution of carbonization and activation are shown in Fig. 7. The pore volume and BET surface area of activation is 0.79 cm3 g-1 and 1394 m2 g-1 respectively, much higher than the 0.15 cm3 g-1 and 283 m2 g-1 of carbonization. The strong nitrogen adsorption of activation showed an Ⅰ-type adsorption-desorption isothermal

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curve (Fig.7a). The adsorption occurred mainly at low pressure, and the pore diameter distribution mainly happened at micropore but showed an obvious peak at mesopore, which illustrates the hierarchically porous structure of the material (Fig. 7b). The specific structure is

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important for electrochemical property.

Heating rate is a key factor for the final electrochemistry performance of the sample. 10 oC

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min-1 was set in the initial phase which led to poor capacitance (Fig S3). 5 oC min-1 was set as the final heating rate through exploration and research because the higher rate leads to insufficient

obvious improvement to the product.

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carbonization and activition whereas the lower rate extends the research period but brings no

With large surface and specific one-dimensional tube structure, the products exhibit a good performance on electrochemistry. A specific capacitance of 256.5 F g-1 is achieved at scan rates

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of 5 mV s-1 within a potential of -0.8 ~ 0.6 V in 6 M KOH. Electrochemical impedance spectroscopy (EIS) was used to reveal the ionic and electronic transport process (Fig. 8b). The real axis intercept represents the equivalent series resistance, which is a combination of ionic

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resistance of the electrolyte, electrical resistance of the electrode and contact resistance at active material/current collector interface,[40] and the radius of the semicircle impedance loop

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represents charge-transfer resistance in the electrode materials. In terms of the EIS results, the Nyquist plot shows an intercept at the real impedance (Z’) of 0.16 Ω, indicating a very low equivalent series resistance. Charge transfer resistance of 0.103 Ω was calculated from the radius of the semicircle in the high-frequency region. In the low-frequency region, the Nyquist plot is a straight line for an EDLC supercapacitor which behaves as an ideal capacitor.

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Fig. 8. Cyclic voltammetry curve recorded at different scan rates over a potential range from -0.8 to 0.6 V (a) and Nyquist plots in the frequency range from 0.1 Hz to 100 k Hz. The inset shows an equivalent electric circuit. 4. Conclusions

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In summary, one-dimensional hierarchically porous carbon was prepared from natural plant

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metaplexis japonica. High surface area and high porosity carbon material was obtained after carbonization and activation. The material exhibits specific capacitance of 256.5 F g-1 and a relatively low equivalent series resistance (0.16 Ω) in 6 M KOH. Hierarchical porosity and large surface area lead to high performance capacitance, whereas the one-dimensional structure is beneficial for charge transfer and causes low ESR. Acknowledgement

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This work was supported by the Natural Science Foundation of China (Grant No. 21621001 and 21371069), the National Key Research and Development Program of China (Grant No.

Province of China (No. 20160101325JC). References

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2016YFB0701100), the 111 project (No. B17020) and the S&T Development Program of Jilin

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ACCEPTED MANUSCRIPT HIGHLIGHTS Biomass-derived one-dimensional hierarchical pore carben (1-DHPC) was synthesized.

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The specific structure is conducive to the diffusion of the charges. Good capacitance of 256.5 F g-1 and low equivalent series resistance of 0.16 Ω

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was obtained.