Graphitized lignin-based activated carbon fibers and their application in supercapacitors

doi:10.21203/rs.3.rs-2223092/v1

Download PDF

Research Article

Graphitized lignin-based activated carbon fibers and their application in supercapacitors

https://doi.org/10.21203/rs.3.rs-2223092/v1

This work is licensed under a CC BY 4.0 License

Version 1

posted

You are reading this latest preprint version

As an abundant bioresource of carbon, lignin has the potential to form carbon fibers (CFs), which can then be used as electrode materials in supercapacitors. However, most studies have only focused on the morphology of CFs, such as the specific surface area and pore-size distribution, while ignoring the influence of the carbon structure in CFs. In this study, Ni(acac)₂ was used as a graphitization catalyst in CFs preparation and to further modify the morphology of the fibers. Meanwhile, the addition of Ni(acac)₂ remarkably shortened the thermostabilization period from 76 h to 2.25 h, which significantly reduced the energy consumption. The resulting lignin-based activated carbon fibers (LACFs) with graphitized structures presented a controllable pore-size distribution and large surface areas up to 582.7 m² g^− 1. These LACFs were then used as electrode materials in supercapacitors, and the assembled devices displayed high energy and power densities of up to 22.1 Wh kg^− 1 and 239 kW kg^− 1, respectively, using organic electrolytes.

Lignin

Activated carbon fibers

Catalytic graphitization

Supercapacitor

Electrochemical performance.

Carbon fibers (CFs) are a type of value-added, lightweight, advanced reinforcement material that can be applied in numerous scenarios, such as in automobiles and aircraft (Agarwal et al., 2020; Khalil, 2017; Patel et al., 2018). In the last decade, CFs have been further developed as electrode materials in energy storage devices because of their continuous porous morphology and large surface area (Chung, 2018; He et al., 2013). However, most CF precursors are petroleum-based polymers such as Polyacrylonitrile (PAN) and pitch, which are unsustainable and expensive (Xu et al., 2020). Therefore, the development of renewable resource-based alternatives is necessary.

Lignin is not only the most abundant natural bioresource after cellulose but also a major byproduct in the pulping industry and in bioethanol production. Compared to other renewable carbon sources, such as cellulose, lignin has a very high carbon content of over 60%, resulting in a high yield of carbonaceous products (Baker and Rials, 2013; Souto et al., 2018). However, most lignin is subjected to low-value combustion for energy recovery. If lignin is used as the precursor in CF production, the cost will decrease to $2.86 USD/lb, which is only one-third the cost of petroleum-based CFs (Poursorkhabi et al., 2020). Thus, lignin is a promising raw material for obtaining low-cost CFs, providing an alternative to conventional CFs in various applications, making it a value-added resource.

Supercapacitors are characteristic energy storage devices that exhibit higher energy densities than conventional capacitors but lower energy densities than batteries (Iro et al., 2016; Saikia et al., 2020; Zhang et al., 2019). Lignin-based carbon fibers (LCFs) can be designed as electrode materials for manufacturing low-cost supercapacitors with high electrochemical performance. According to the equation C = εA/d, high-capacitance (C) supercapacitors from CFs should contain electrodes with large specific surface areas (A) and an optimum distance (d) between the charged electrode and counter electrolyte ions, which is typically related to the hierarchical porous structure (Bruno et al., 2010; Cheng et al., 2021; Guo et al., 2021; Wang et al., 2020). However, the dielectric constant, ε, is a complex parameter that is mainly related to electrode materials, and its influence has rarely been studied. In the case of all-carbon electrodes, the value of ε is closely related to the structure of the carbon allotropes: graphite (carbon crystal) shows an ε value of 37.9 with a perfect conductive network; carbon black containing turbostatic carbon structures has ε values 2.5–3.0, whereas charcoal (amorphous carbon) has ε values of only 1.2–1.81 (Haynes et al., 2016). Thus, further improvement to the capacitance of supercapacitors from lignin can be expected when the LCFs contain a large ratio of graphitic carbon. Conventional graphitization is carried out at extremely high temperatures between 2000 and 3000°C (Ramos et al., 2013). Thus, there is an urgent need to develop a facile method to produce graphitized porous LCFs for supercapacitors.

To prepare low-cost, high-performance LCFs, our study was carried out as shown in Fig. 1. Lignin/nickel acetate fibers were fabricated using an electrospinning technique, followed by fast thermostabilization. With the addition of the nickelous catalyst, carbonization and catalytic graphitization were carried out simultaneously at relatively low temperatures. An additional activation process was also carried out to optimize the surface area and pore-size distribution of lignin-based activated carbon fibers (LACFs). Finally, supercapacitors were assembled using the LACFs, and their electrochemical properties were characterized.

Materials

Technical acetic acid lignin from bamboo was kindly provided by Yinnovator Biotech Co. Ltd. (Guangzhou, China). Nickel(II) acetylacetonate [Ni(acac)₂, 95%] was purchased from Aladdin Biochemical Technology Co. Ltd. (Shanghai, China). N-Dimethyl formamide (DMF), potassium hydroxide (KOH), poly epoxidized ethylene (PEO) (Mv = 600 kDa), carboxymethyl cellulose sodium (CMC), and carbon black (CB) were purchased from Macklin Biochemical Co. Ltd. (Shanghai, China). Triethylmethylammonium tetrafluoroborate (TEMABF₄) and dimethyl carbonate (PC) were purchased from TCI (Shanghai) Development Co., Ltd. All reagents were used as received.

Preparation Of Lignin Fibers

Hot water-washed lignin and PEO (99:1, w/w) were dissolved in DMF with different amounts of Ni(acac)₂ to prepare homogeneous solutions. The as-prepared solutions were then electrospun into lignin fibers (LFs) using an electrospinning apparatus (TL-03; Tongli Co., LTD, Shenzhen, China). The electrospinning conditions were as follows: syringe needle type, 21-gauge needle; working voltage, 18 kV; flow rate, 0.3 mL h^− 1; needle–collector distance, 15 cm; temperature, 30–40 ℃; humidity, 30–45%.

Thermal Treatment Of Lfs

Thermal treatment, including thermostabilization, carbonization, and activation, was carried out to transform the electrospun LFs to LACFs (GSL-1600X, Hefei Kejing Material Technology Co., LTD, China). The LFs were first stabilized at 250°C under air atmosphere for 1 h to obtain lignin-based thermostabilized fibers (LSFs). The applied heating rates were 0.05°C min^− 1 and 3°C min^− 1 for fibers with and without Ni(acac)₂, respectively. Subsequently, the LSFs were carbonized at 1400°C for 1 h under N₂ atmosphere at a heating rate of 3°C min^− 1 to generate LCFs. Finally, LACFs were achieved via KOH activation (LCFs/KOH in a weight ratio of 1:4) at 900°C for 1 h under N₂ atmosphere at a heating rate of 10°C min^− 1. All the LACFs were neutralized using diluted HCl and washed with deionized water before use. The LF, LSF, LCF, and LACF samples are denoted as LF-x, LSF-x, LCF-x, and LACF-x, where x refers to 0, 1, 2, and 5% Ni(acac)₂, respectively.

Electrode Preparation And Supercapacitor Assembly

A mixture of ground LACFs and CB was poured into a 2% CMC aqueous solution to prepare electrode material slurries (LACFs:CB:CMC, 85:5:10 by weight). The slurries were then coated on Al foil, which was dried and cut into circular sheets to work as electrodes (diameter, 16 mm). To assemble the supercapacitor, 1M TEMABF₄/PC served as the electrolyte and cellulosic paper (NKK TF4030, Japan) was used as the separator.

Morphology Analysis

The morphological analysis of the fibers was conducted using scanning electron microscopy (SEM; S4800, Hitachi, Japan) at an accelerating voltage of 5 kV after gold sputtering. N₂ adsorption/desorption measurements at -196°C were performed using a surface area and porosity analyzer (ASAP2460, Micromeritics, USA). The specific surface area and porosity were analyzed based on the adsorption isotherms. The internal and external specific surface areas were calculated using the t-plot method in a relative pressure range of 0.2–0.5. The pore-size distribution was calculated using the NLDFT model.

Carbonaceous Structure Analysis

The structural variations of the LCFs and LACFs were identified using X-ray diffraction (XRD; D8 Advance, Bruker, Germany). XRD patterns were collected in the 2θ range of 10–60° using Cu Kα radiation operated at 40 kV and 40 mA.

The structures of the sample surfaces were characterized using a DXR2 Raman microscope (Thermo Scientific DXRxi, Thermo Fisher Scientific, USA) at room temperature. The excitation wavelength from a diode-pumped solid-state laser was 532 nm. The laser power was 0.1 mW to avoid overheating the surfaces of the samples. The in-plane size (L_a) was calculated using the following equation (You et al., 2018):

L _a = 2.4 × 10^− 10 λ⁴R⁻¹ (1)

where λ is the laser wavelength (nm) and R is the integrated area ratio of the D-band (1350 cm^− 1) to the G-band (1600 cm^− 1) in the Raman spectra.

Powdered LCFs and LACFs were dispersed in ethanol, and a droplet of supernatant was placed on a lacy copper grid for fine structural observation under a transmission electron microscope (TEM; Tecnai G2 f20 TWIN 200 kV, FEI, USA). The interlayer spacing (d₀₀₂) of the graphitic region was calculated using the Bragg equation (Khani and Moradi, 2013).

$${d}_{002}=\frac{\lambda }{2\text{sin}\theta }$$

Electrochemical Performance

The electrical performance of the assembled supercapacitors was evaluated using an electrochemical workstation (Donghua DH7000, Donghua Analytical Instrument Co., Ltd., China). Electrochemical impedance spectroscopy (EIS) experiments were performed in the frequency range of 10⁶ Hz to 1 Hz with a potential amplitude of 10 mV. The cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) processes were monitored at various scan rates from 0.05 to 0.2 V s^− 1 and a current density of 0.5 A g^− 1, respectively. For the CV measurements, the gravimetric capacitance (C) was obtained using Eq. 3 (Vicentini et al., 2021; You et al., 2015).

C $=\frac{4\bullet \int i dV}{m\bullet v\bullet \varDelta E}$ (3)

where m is the material loading weight of the two electrodes, ΔE is the voltage window, i is the response current, and v is the scan rate. For the GCD-based capacitance calculation, the specific capacitance (C), energy density (E), and power density (P) were calculated using the following equations (Kim et al., 2013; Vicentini et al., 2021):

C $=\frac{4i}{mdV/dt}$ (4)

$$E=\frac{1}{8}C{{V}_{max}}^{2}$$

$$P=\frac{({V}_{max}-{V}_{drop}{)}^{2}}{4{mR}_{s}}$$

where i is the current density and dV/dt is the slope of the discharge curve. R_s is the equivalent series resistance obtained from the EIS profiles. V_max and V_drop are the maximum operating potential difference and voltage drop during discharge initiation, respectively.

Morphology characterization

Figure 2 shows the morphological transformation from LFs to LACFs in the electrospinning, thermostabilization, carbonization, and activation processes. All the LFs and LSFs with various amounts of Ni(acac)₂ present smooth surfaces, indicating a good spinning system for lignin/PEO/Ni(acac)₂. With increasing Ni(acac)₂ content, the diameter of the LFs gradually decreased from 2.17 ± 0.81 µm for LF-0 to 1.43 ± 0.56 µm for LF-5 (Table S1). LF-0 was able to maintain the fiber form at the maximum heating rate of 0.05°C min^− 1. Remarkably, LF-1, LF-2, and LF-5 transformed to LSFs at 2°C min^− 1, suggesting that the thermostabilization time was shortened from 76 h to 2.25 h owing to the addition of Ni(acac)₂. After carbonization, the diameter of the LCFs decreased further, and the surface became more porous as the Ni(acac)₂ content increased. Even though PEO was able to generate pores owing to its decomposition during carbonization, the changes in these pores among the LCFs can more likely be attributed to the addition of Ni(acac)₂, which indicates that the nickel catalyst assisted pore formation. KOH activation was performed to further increase the porosity of the LCFs for supercapacitor electrode applications. As shown in Figs. 2m–p, the diameter of the resultant LACFs decreased to 220 nm, and the surface was highly etched by KOH.

Structural Determination

To understand the carbon structure from both bulk and surface views, the LCF and LACF samples were studied using XRD and Raman spectroscopy. As shown in Fig. 3a, there were no obvious diffraction peaks in the spectra of LCF-0, indicating that LCF-0 predominantly contained amorphous carbon with a few crystalline structures. With increasing Ni(acac)₂ content, the intensities of the characteristic peaks at 26° and 46° both increased, revealing the formation of the hexagonal (002) crystal plane and rhombohedral (102) crystal plane of graphite, respectively (Inagaki and Kang, 2014). The mechanism can be explained as follows: Ni(acac)₂ first decomposes into nickel particles at elevated temperatures. According to the Ni–C(graphite) phase diagram, a certain amount of carbon dissolves in the nickel at temperatures above 1326.5°C, becoming saturated when the C/Ni solution concentration is above 2.7 at.%. Thus, graphitic carbon spontaneously dissolved out because the Gibbs free energy change from disordered carbon to graphite is negative (Kim et al., 2016; Singleton and Nash, 1989). Maintaining the graphitic (002) crystal plane, the diffraction peak shifted from 46° to 44° after activation, which is indexed to turbostatic (101) plane formation (Fig. 3b). These characteristic peaks were even sharper, indicating that both the graphitic and turbostatic structures were well developed. Among the LACFs, the peaks of LACF-2 showed much higher intensities than those of LACF-5, which might have been caused by the excess KOH etching-induced graphitic structure collapse.

Table 1

R and L_a values of the LCFs and LACFs
Samples	R = I_D/I_G	L_a (nm)
LCF-0	3.47	5.53
LCF-1	2.14	8.98
LCF-2	2.03	9.43
LCF-5	2.05	9.37
LACF-0	2.07	9.31
LACF-1	1.22	15.7
LACF-2	0.85	22.7
LACF-5	0.98	19.6

The carbonaceous structures on the surfaces of the LCFs and LACFs were detected using Raman spectroscopy. The spectra shown in Figs. 3c–d were first deconvoluted, and the calculated results are shown in Table 1. The D-band at 1350 cm^− 1 indicates disordered carbon, and the typical G-band at 1600 cm^− 1 represents the graphitic structure (You et al., 2018). With increasing Ni(acac)₂ content, the value of R decreased from 3.47 for LCF-0 to a minimal value of approximately 2.04 for LCF-2 and LCF-5. L_a also increased as an indicator of graphitic crystallite size. In addition, distinct 2D bands at 2700 cm^− 1, indicative of graphite layers, were observed in all samples containing the nickelous catalyst. These results indicate that the addition of Ni(acac)₂ was conducive to the formation of graphitic carbon on the surfaces of the LCFs. After activation, the R value for LACF-2 decreased to 0.85, suggesting that the activation process had a greater influence in terms of facilitating the formation of graphitic carbon rather than destroying the ordered structure on the surfaces of the LACFs.

To further verify the formation of the graphitic structure, the LCFs and LACFs were observed by TEM (Fig. 4). Similar to the XRD and Raman results, LCF-0 and LACF-0 only displayed a disordered microstructure, suggesting typical amorphous carbon. With the addition of Ni(acac)₂, both a regular graphite layer and amorphous carbon were present in the carbon fiber. The ordered layered structure became thicker, such that LCF-5 achieved a maximum thickness of approximately 4.5 nm. The measured spacing between the crystal layers was 0.34 nm, which is consistent with the distance between neighboring layers of graphite (d₀₀₂) (Inagaki and Kang, 2014). After activation, an ordered structure developed in all the LACF samples. Specifically, LACF-2 showed a better graphitized structure than LACF-5, which proves that KOH etching induced structural collapse.

Table 2

Textural properties of LCFs and LACFs with various Ni(acac)₂ contents
Samples	S_BET ^a (m² g^− 1)	W_p ^b (nm)	V_total ^c (cm³ g^− 1)	S_internal ^d (m² g^− 1)	S_external ^e (m² g^− 1)
LCF-0	150.41	5.79	0.22	37.26	114.81
LCF-1	183.58	5.23	0.24	78.75	107.57
LCF-2	265.46	4.38	0.29	157.40	110.69
LCF-5	360.53	4.67	0.42	182.53	182.54
LACF-0	389.80	3.80	0.37	101.01	288.79
LACF-1	280.48	3.86	0.27	85.81	194.67
LACF-2	582.70	3.38	0.49	240.12	342.58
LACF-5	460.66	4.66	0.40	268.06	192.60
^a S_BET: Specific surface area computed using Brunauer–Emmett–Teller (BET) equation;
^b W_p: The adsorption average pore width;
^c V_total: Total pore volume;
^d S_internal: Surface area of micropores and mesopores using t-plot method;
^e S_external: Surface area of macropores using t-plot method.

Nitrogen adsorption/desorption measurements were performed to track the surface area and pore-size distribution of the LCFs and LACFs. As displayed in Table 2, LCF-0 showed a small specific surface area of 150.41 m² g^− 1 and a low pore volume of 0.22 cm³ g^− 1. With increasing amounts of nickelous catalyst, both the surface area and pore volumes increased, reaching maximum values for LCF-5. This can be attributed to the structural differences of the LCFs: LCF-0 formed disordered carbon when subjected to thermal treatment, whereas LCF-5 was the most catalyzed and generated the highest amount of graphitic carbon in the amorphous carbon phase. The amorphous carbon region was relatively thermally unstable and easily decomposed during carbonization compared with the graphite region (Akhtar et al., 2016; Han et al., 2016). Thus, the surface area and roughness increased as the Ni(acac)₂ content increased. The subsequent activation process effectively increased the specific surface area and created more pores in the LACFs. The surface area of LACF-2 reached a maximum value of 582.7 m² g^− 1, but it decreased to 460.7 m² g^− 1 for LACF-5. Based on the t-plot method, LACF-2 and LACF-5 both developed micropores and mesopores after activation, which resulted in similar increasing S_internal values from the LCFs to the corresponding LACFs. However, the S_external value of LACF-5 was lower than that of LACF-2, which indicates that KOH etching-induced structural collapse mainly occurred for macroporous samples with high nickel contents. Accordingly, Ni(acac)₂ addition was conducive not only to the formation of a graphitic structure but also to the increased surface area and adjusted pore-size distribution of the LCFs and LACFs.

Electrochemical Tests

The electrochemical behavior of the LCF and LACF electrodes was measured in a 1M TEMABF₄/PC electrolyte solution using a two-electrode system. The Nyquist plots shown in Fig. 5a exhibit a semicircle in the high-frequency region and a straight line in the low-frequency region. As shown in Fig. 5a, the electrode resistance (R_e), which is assigned to the resistance of the electrode materials and their contacts, was obtained from the intercept at the real axis in the high-frequency region. The equivalent series resistance (R_s), as a measure of the sum of the electrode and electrolyte resistances, was obtained from the intersection between the straight line and Z_re axis (Mei et al., 2018). Owing to the well-developed graphitic structure, supercapacitors fabricated from LACF-2 and LACF-5 displayed low R_e values of approximately 0.8 Ω, which is much smaller than that of LACF-0 (8.3 Ω). In addition, the straight line in the low-frequency region indicates a diffusion control step, and the high slopes of the LACF electrodes at low frequencies indicate rapid diffusion of electrolyte ions. These results indicate that the LACF electrodes, especially the LACF-2 and LACF-5 electrodes, had high conductivity and good diffusion ability for electrolyte ions during the charge and discharge processes.

The CV curves of all the LACFs electrodes were approximately rectangular at all scan rates, indicating typical supercapacitor behavior (Fig. 5b). The specific capacitance of LACF-0 was 29.2 F g^− 1 at a scan rate of 0.05 V s^− 1. With increasing Ni(acac)₂ content, the capacitance gradually increased, achieving the maximum value of 74.6 F g^− 1 for LACF-2, which can be attributed to the large surface area and facile pore accessibility of the electrolyte ions in the electrode.

Table 3

Summary of supercapacitor performance using different LACF electrodes
Samples	C_CV ^a (F g^− 1)	C_GCD ^b (F g^− 1)	R_s ^c (Ω)	E ^d (Wh kg^− 1)	P ^e (kW kg^− 1)
LACF-0	27.0	15.6	9.15	4.89	92.3
LACF-1	29.2	45.7	3.06	11.5	303
LACF-2	74.6	70.7	1.67	22.1	239
LACF-5	46.0	51.7	2.35	16.1	263
^a C_CV: Specific calculated from CV profiles;
^b C_GCD: Specific calculated from GCD profiles;
^c R_s: Equivalent series resistance from Nyquist plots;
^d E: Energy density;
^e P: Power density.

GCD measurements were carried out at a current density of 0.5 A g^− 1 to further evaluate the electrochemical performance of the LACFs. Similar to the CV results, the IR drop of the LACF-0 electrode was 0.4 V, whereas the supercapacitor fabricated using LACF-2 using the same recipe displayed an IR drop of only 0.005 V (Fig. 5c). The GCD capacitance increased from 42.3 F g^− 1 for LACF-0 to 70.9 F g^− 1 for LACF-2. Thus, the supercapacitor fabricated using LACF-2 showed a high energy density of 22.1 Wh kg^− 1 and a power density of 239 kW kg^− 1, values that are comparable to those of supercapacitors derived from lignin and other bioresources in previous studies (Tables 3 and 4). In addition, the capacitance was maintained at over 94% after 500 charge/discharge cycles (Fig. 5d). Therefore, the improvement in electrochemical performance can be attributed to the larger surface area, proper pore-size distribution, and rich graphitic structure of LACF-2 owing to the addition of Ni(acac)₂.

Table 4

Electrochemical performance of assembled supercapacitors using carbonaceous electrodes derived from bioresources
Electrode materials	Electrolyte	Energy density (Wh kg^-1)		Ref.
Lignin/PAN-derived carbon nanofibers	6M KOH	9.3	0.5	(Dai et al., 2019)
Activated lignocellulosic carbon	6M KOH	6.5	3.4	(Huang et al., 2014)
Lignin/PAN/pitch-derived carbon nanofibers with ZnO	6M KOH	22	0.4	(Yun et al., 2019)
Lignin-derived activated carbon fibers	6M KOH	4	52	(Schlee et al., 2019)
Lignin-derived carbon fibers	6M KOH	8.4	60	(Schlee et al., 2019)
Lignin/cellulose acetate-derived carbon nanofibers	6M KOH	31.5	0.4	(Xu et al., 2021)
N/O co-doped carbon nanofibers	1M Na₂SO₄	17.9	0.8	(Dai et al., 2020)
Wood sawdust and tannic acid-derived porous carbon	1M TEABF₄/AN	20	26	(Sevilla et al., 2019)
Waste coffee grounds-derived nanoporous carbon	1M TEABF₄/AN	20.1	0.7	(Poochai et al., 2021)
Tobacco rod-derived carbon	1M TEABF₄/AN	31.3	11.8	(Zhao et al., 2016)
Raw hemp stem-derived activated carbon	1M TEABF₄/PC	19.8	21	(Sun et al., 2016)
Tubular kapok fiber-derived mesoporous carbon flakes	1M TEABF₄/PC	24	24	(Zou et al., 2019)
This work	1M TEMABF₄/PC	22.1	239

A feasible and fast LACF preparation process was developed using Ni(acac)₂, and its influence on the morphological, structural, and electrochemical properties of the resultant fibers was addressed in this study. With the help of Ni(acac)₂, the diameter of the LFs decreased, and the thermostabilization period was remarkably shortened from 76 h to 2.25 h, which significantly lowers the cost of LACF production. In the subsequent carbonization and activation processes, conductive carbon structures were generated both inside and on the surfaces of the LCFs and LACFs owing to catalytic graphitization. Interestingly, the surface area of the LACFs increased to 582.7 m² g^− 1, and the pore-size distribution was optimized with the addition of Ni(acac)₂. Benefiting from the porous and conductive structure of the LACFs, a supercapacitor fabricated using LACF-2 displayed a high energy density of 22.1 Wh kg^− 1 and a power density of 239 kW kg^− 1 using an organic electrolyte, which is comparable to the performance of supercapacitors in previous studies. Considering the cost–performance balance, LACFs assisted by Ni(acac)₂ are an attractive approach for preparing high-performance supercapacitors.

Acknowledgements

The authors gratefully acknowledge financial support from National Natural Science Foundation of China (31901264 and 22002079) and Research Start-up Fund of the Shaanxi University of Science & Technology (2018-BJ20).

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

Agarwal J, Sahoo S, Mohanty S, Nayak SK (2020) Progress of novel techniques for lightweight automobile applications through innovative eco-friendly composite materials: A review. J Thermoplast Compos Mater 33:978-1013
Akhtar K, Tahmasebi A, Tian L, Yu J, Lucas J (2016) An experimental study of direct reduction of hematite by lignite char. J Therm Anal Calorim 123:1111-1118
Baker DA, Rials TG (2013) Recent advances in low‐cost carbon fiber manufacture from lignin. J Appl Polym Sci 130:713-728
Bruno MM, Cotella NG, Miras MC, Koch T, Seidler S, Barbero C (2010) Characterization of monolithic porous carbon prepared from resorcinol/formaldehyde gels with cationic surfactant. Colloids Surf A 358:13-20
Cheng T, Zhang YZ, Wang S, Chen YL, Gao SY, Wang F, Lai WY, Huang W (2021) Conductive Hydrogel-Based Electrodes and Electrolytes for Stretchable and Self-Healable Supercapacitors. Adv Funct Mater 31:2101303
Chung D (2018) Development design and applications of structural capacitors. Appl Energy 231:89-101
Dai Z, Ren PG, He W, Hou X, Ren F, Zhang Q, Jin YL (2020) Boosting the electrochemical performance of nitrogen-oxygen co-doped carbon nanofibers based supercapacitors through esterification of lignin precursor. Renew Energy 162:613-623
Dai Z, Ren PG, Jin YL, Zhang H, Ren F, Zhang Q (2019) Nitrogen-sulphur Co-doped graphenes modified electrospun lignin/polyacrylonitrile-based carbon nanofiber as high performance supercapacitor. J Power Sources 437:226937
Guo W, Yu C, Li SF, Qiu JS (2021) Toward commercial-level mass-loading electrodes for supercapacitors: opportunities, challenges and perspectives. Energy Environ Sci 14:576-601
Han H, Jiang C, Huo L, Gao J (2016) Mechanical and thermal properties of cationic ring-opening o-cresol formaldehyde epoxy/polyurethane acrylate composites enhanced by reducing graphene oxide. Polym Bull 73:2227-2244
Haynes WM, Lide DR, Bruno TJ (2016) CRC Handbook of Chemistry and Physics, 97th edn. CRC Press, Boca Raton
He Y, Chen W, Gao C, Zhou J, Li X, Xie E (2013) An overview of carbon materials for flexible electrochemical capacitors. Nanoscale 5:8799-8820
Huang C, Puziy AM, Sun T, Poddubnaya OI, Suárez-García F, Tascón JMD, Hulicova-Jurcakova D (2014) Capacitive Behaviours of Phosphorus-Rich Carbons Derived from Lignocelluloses. Electrochim Acta 137:219-227
Inagaki M, Kang F (2014) Fundamental Science of Carbon Materials. In: Inagaki M, Kang F (ed) Materials Science and Engineering of Carbon: Fundamentals, 2nd edn. Butterworth-Heinemann, Oxford, pp 17-217
Iro ZS, Subramani C, Dash S (2016) A brief review on electrode materials for supercapacitor. Int J Electrochem Sci 11:10628-10643
Khalil YF (2017) Eco-efficient lightweight carbon-fiber reinforced polymer for environmentally greener commercial aviation industry. Sustain Prod Consum 12:16-26
Khani H, Moradi O (2013) Influence of surface oxidation on the morphological and crystallographic structure of multi-walled carbon nanotubes via different oxidants. J Nanostructure Chem 3:73
Kim T, Jung G, Yoo S, Suh KS, Ruoff RS (2013) Activated Graphene-Based Carbons as Supercapacitor Electrodes with Macro- and Mesopores. ACS Nano 7:6899-6905
Kim T, Lee J, Lee KH (2016) Full graphitization of amorphous carbon by microwave heating. RSC Advances 6:24667-24674
Mei BA, Munteshari O, Lau J, Dunn B, Pilon L (2018) Physical Interpretations of Nyquist Plots for EDLC Electrodes and Devices. J Phys Chem C 122:194-206
Patel M, Pardhi B, Chopara S, Pal M (2018) Lightweight composite materials for automotive-a review. Carbon 1:151
Poochai C, Srikhaow A, Lohitkarn J, Kongthong T, Tuantranont S, Tuantranont S, Primpray V, Maeboonruan N, Wisitsoraat A, Sriprachuabwong C (2021) Waste coffee grounds derived nanoporous carbon incorporated with carbon nanotubes composites for electrochemical double-layer capacitors in organic electrolyte. J Energy Storage 43:103169
Poursorkhabi V, Abdelwahab MA, Misra M, Khalil H, Gharabaghi B, Mohanty AK (2020) Processing, carbonization, and characterization of lignin based electrospun carbon fibers: a review. Front Energy Res 8:208
Ramos A, Cameán I, García AB (2013) Graphitization thermal treatment of carbon nanofibers. Carbon 59:2-32
Saikia BK, Benoy SM, Bora M, Tamuly J, Pandey M, Bhattacharya D (2020) A brief review on supercapacitor energy storage devices and utilization of natural carbon resources as their electrode materials. Fuel 282:118796
Schlee P, Herou S, Jervis R, Shearing PR, Brett DJL, Baker D, Hosseinaei O, Tomani P, Murshed MM, Li YM, Mostazo-Lopez MJ, Cazorla-Amoros D, Sobrido ABJ, Titirici MM (2019) Free-standing supercapacitors from Kraft lignin nanofibers with remarkable volumetric energy density. Chem Sci 10:2980-2988
Schlee P, Hosseinaei O, Baker D, Landmér A, Tomani P, Mostazo-López MJ, Cazorla-Amorós D, Herou S, Titirici MM (2019) From Waste to Wealth: From Kraft Lignin to Free-standing Supercapacitors. Carbon 145:470-480
Sevilla M, Diez N, Ferrero GA, Fuertes AB (2019) Sustainable supercapacitor electrodes produced by the activation of biomass with sodium thiosulfate. Energy Stor Mater 18:356-365
Singleton M, Nash P (1989) The C-Ni (Carbon-Nickel) system. Bull Alloy Phase Diagr 10:121-126
Souto F, Calado V, Pereira N (2018) Lignin-based carbon fiber: A current overview. Mater Res Express 5:072001
Sun W, Lipka SM, Swartz C, Williams D, Yang F (2016) Hemp-derived activated carbons for supercapacitors. Carbon 103:181-192
Vicentini R, Aguiar JP, Beraldo R, Venâncio R, Rufino F, Da Silva LM, Zanin H (2021) Ragone Plots for Electrochemical Double-Layer Capacitors. Batteries Supercaps 4:1291-1303
Wang J, Zhang X, Li Z, Ma Y, Ma L (2020) Recent progress of biomass-derived carbon materials for supercapacitors. J Power Sources 451:227794
Xu Y, Chen S, Zhu M, Liu Y (2021) Novel silicon-contained lignin-based carbon fibers derived from bamboo pulping black liquor with improved electrochemical performance for supercapacitors. J Appl Polym Sci 138:51321
Xu Y, Liu Y, Chen S, Ni Y (2020) Current overview of carbon fiber: Toward green sustainable raw materials. BioResources 15:7234-7259
You X, Misra M, Gregori S, Mohanty AK (2018) Preparation of an electric double layer capacitor (EDLC) using Miscanthus-derived biocarbon. ACS Sustain Chem Eng 6:318-324
You XY, Koda K, Yamada T, Uraki Y (2015) Preparation of electrode for electric double layer capacitor from electrospun lignin fibers. Holzforschung 69:1097-1106
Yun SI, Kim SH, Kim DW, Kim YA, Kim BH (2019) Facile preparation and capacitive properties of low-cost carbon nanofibers with ZnO derived from lignin and pitch as supercapacitor electrodes. Carbon 149:637-645
Zhang K, Liu M, Zhang T, Min X, Wang Z, Chai L, Shi Y (2019) High-performance supercapacitor energy storage using a carbon material derived from lignin by bacterial activation before carbonization. J Mater Chem A 7:26838-26848
Zhao YQ, Lu M, Tao PY, Zhang YJ, Gong XT, Yang Z, Zhang GQ, Li HL (2016) Hierarchically porous and heteroatom doped carbon derived from tobacco rods for supercapacitors. J Power Sources 307:391-400
Zou Z, Liu T, Jiang C (2019) Highly mesoporous carbon flakes derived from a tubular biomass for high power electrochemical energy storage in organic electrolyte. Mater Chem Phys 223:16-23

No competing interests reported.

2SupplementaryInformation.docx

Download PDF

Version 1

posted

You are reading this latest preprint version

Graphitized lignin-based activated carbon fibers and their application in supercapacitors

Status:

Version 1

Abstract

Figures

Introduction

Material And Methods

Materials

Preparation Of Lignin Fibers

Thermal Treatment Of Lfs

Electrode Preparation And Supercapacitor Assembly

Morphology Analysis

Carbonaceous Structure Analysis

Electrochemical Performance

Results And Discussion

Morphology characterization

Structural Determination

Electrochemical Tests

Conclusion

Declarations

Acknowledgements

Conflict of interest

References

Additional Declarations

Supplementary Files

Status:

Version 1