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Biomass porous carbon derived from jute fiber as anode materials for lithium-ion batteries
Diamond & Related Materials 98 (2019) 107514
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Biomass porous carbon derived from jute fiber as anode materials for lithium-ion batteries ⁎
Yanli Doua, Xin Liua, Kaifeng Yua, Xiaofeng Wangb, Weiping Liuc, Jicai Lianga,d, , Ce Lianga,
T ⁎⁎
a
Key Laboratory of Automobile Materials, Ministry of Education, College of Materials Science and Engineering, Jilin University, Changchun 130025, China State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130025, Jilin, China c College of Instrumentation and Electrical Engineering, Jilin University, Changchun 130025, Jilin, China d Roll Forging Research Institute, Jilin University, Changchun 130025, Jilin, China b
A R T I C LE I N FO
A B S T R A C T
Keywords: Jute fiber Biomass Porous carbon Anode Lithium-ion battery
Porous carbon derived from jute fiber through a convenient approach has been explored as an anode for lithiumion batteries. High BET surface area of 2043.528 m2 g−1 and porous structure of carbon is obtained by CuCl2 activation. The resulting carbonaceous material exhibits excellent specific charge capacity as high as 580.4 mA h g−1 at the current density of 0.2C after 100 cycles. This research can provide a novel route for the production of high performance energy storage materials from biomass wastes.
1. Introduction With the consumption of fossil fuel and global warming, concerns of the energy and environment have increased in recent years. Meanwhile, population and economic growth are leading to the increasing need of energy storage [1,2]. It is well known that lithium-based technology is the most promising storage system as of today. Lithium ion batteries (LIBs) are widely used by portable electronic devices and electric vehicles (EVs) in people's life [3] due to its high energy density, long cycle life and light weight. Generally, graphite is the most popular anode material for LIBs because of its high density, promising electrical conductivity and excellent cycle stability [4]. However, the limited capacity of graphite carbon used for the anode materials in lithium batteries is only 372 mA h g−1 [5]. Due to its limited specific capacity, new carbon materials should be developed for high performance electrode. Besides, considering the environmental issue and economic cost, ideal electrode materials should be derived from renewable resources. To prepare superior electrode material, activated carbon from biomass such as bamboo wood, bamboo char, microalgae, rice husk and peanut skin were used as precursor materials [6–12]. Yu et al. [13] used sisal fibers to prepare activated carbon anode for lithium-ion batteries, which possessed insertion capacity of 646 mA h g−1 from the first cycle at 0.1 C, but exhibited initial coulombic efficiencies of only 41%. The results of these reports give clear support for the lignocellulosic natural
fibers (including sisal fiber, jute fiber and hemp fiber) to make into activated carbon as anode materials. Jute fiber is a kind of biomass extracted from the stem or bast of genus corchorus [14]. The world annual production of the jute is 3600 thousand tones [13]. It is one of the cheapest natural fibers in the world. These kind of natural fibers are made up of crystalline microfibrils based on cellulose (58–63%), which are connected by amorphous lignin (12–15%) and hemicelluloses (20–22%) [15,16]. In the jute fiber, the molecules are highly oriented parallel in the fibrils which are connected with other fibrils. As mentioned before, jute fiber is a carbon source which is low-cost, readily available, widely distributed, environmentally friendly and renewable. Therefore, jute fibers have been chosen to develop for new carbonbased anode materials with high lithium ion storage capacity in our work. As of today, the main methods to make porous structures in carbon includes the activation method [17], template method [18,19], organic gel carbonization method [20] and blend polymer carbonization method [21]. In the chemical method, the CuCl2 activation method is considered to be an effective route for preparing a high specific surface area porous carbon [22,23]. In this study, CuCl2 were used as activation agent based on the following reasons. Firstly, conversion of jute fiber precursors into porous structure carbon occurs during the heatment process of the mixture of CuCl2 and jute fiber after grinding them into powder. Furthermore, porous nature and high surface area of jute fiber
⁎
Correspondence to: J. Liang, Key Laboratory of Automobile Materials, Ministry of Education, College of Materials Science and Engineering, Jilin University, Changchun 130025, China. ⁎⁎ Corresponding author. E-mail addresses: [email protected] (J. Liang), [email protected] (C. Liang). https://doi.org/10.1016/j.diamond.2019.107514 Received 30 April 2019; Received in revised form 3 August 2019; Accepted 12 August 2019 Available online 14 August 2019 0925-9635/ © 2019 Elsevier B.V. All rights reserved.
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Fig. 1. The formation process of porous carbon derived from jute fibers.
Brunauer–Emmett–Teller analysis was performed on Micrometrics ASAP 2420 surface analyzer to obtain specific surface area and pore size distribution of different samples.
carbon have been obtained. In addition, the size and distribution of the pores could be adjusted by the amount of activation agent CuCl2. Beyond characterization of pores size and microstructure, jute fiber carbon was demonstrated to be employed as electrode material with excellent reversible capacity and rate capability. Finally, this method has a hopeful prospect due to its feature of straightforward and cheapness. Therefore, in this study, CuCl2 were used as activation agent based on the above reasons. Firstly, conversion of jute fiber precursors into porous structure carbon occurs during the heating process of the mixture of CuCl2 and jute fiber after grinding them into powder. Furthermore, porous nature and high surface area of jute fiber carbon have been obtained. In addition, the size and distribution of the pores could be adjusted by the amount of activation agent CuCl2. Beyond characterization of pores size and microstructure, jute fiber carbon was demonstrated to be employed as electrode material with excellent reversible capacity and rate capability. Finally, this method has a hopeful prospect due to its feature of straightforward and cheapness.
2.3. Electrochemical measurements Electrochemical property was tested using coin cells (CR2025, half cell) which were assembled in Ar-filled glovebox with moisture and oxygen concentrations below 1 ppm. The carbon electrode was made by coating the slurry of active substance, acetylene black and polyvinyl fluoride (PVDF) at the mass ratio of 8:1:1 dissolved in N-methyl-2pyrrolidone (NMP) on a copper foil and dried in a vacuum oven at 120 °C for 12 h. The electrolyte was 1 mol L−1 LiPF6 in a 50: 50 w/w mixture of ethylene carbonate and diethyl carbonate. The cyclic voltammetry curve and impedance curve were performed on a CHI660C electrochemical workstation. The CV measurements were tested between 0 and 3.0 V at a scan rate of 0.1 mV/s. The EIS measurements were analyzed in the range of 100 kHz to 10 m Hz. The charge–discharge performance were tested between 0.02 V and 3.0 V at a 0.2C (1C = 372 mA/g) rate on a LAND (CT2001A) battery test system.
2. Experimental 2.1. Materials synthesis
3. Results and discussion Jute fibers were washed with deionized water to remove the impurities. And they were cut into small pieces around 3 mm long and mixed with copper chloride at the weight ratio of 1:0, 1:6, 1:8 and 1:10. After fully impregnation by stirring for 12 h and being ultrasonic for 8 h, the samples were dried in the oven at 80 °C. Then they were ground fully in an agate mortar and put in the porcelain boat.(as shown in Fig. S1) The activation process was carried out through heating in the tube furnace at 800 °C for 2 h under argon atmosphere with the heating rate of 2 °C/min. When cooled to room temperature, samples were grinded fully in an agate mortar and washed with 2 M hydrochloric acid solution until the red matter disappeared. After washing to neutral with deionized water, jute fiber activated carbons were denoted as JFC-0, JFC-6, JFC-8 and JFC-10.
Fig. 1 illustrates the material synthesis process applied to the electrodes. Jute fiber has natural fibrous structure providing stacked capillaries to absorb CuCl2, leading to a uniform mixture of them. In the process of activation, CuCl2 is used as activating agent to fulfill the carbonization process according to the Eqs. (1) and (2) [22,24]. It is proved that the X-ray diffraction (XRD) tests on the unwashed resulted product under 800 °C/2 h (Fig. S2.a) and 500 °C/1 h (Fig. S2.b) show the presence of Cu (Fig. S2.a) and CuCl (Fig. S2.b) in the composite. The reactions proceeded with jute fiber carbon and CuCl2 include some simultaneous and continuous reactions. In this process, copper, cuprous chloride and some gases such as carbon dioxide and hydrogen chloride are generated, and pores are formed because of the corrosion on surface. Besides, the further reaction occurs between the intermediate product cuprous chloride and jute fiber carbon, forming more interior pores. As a consequence, the final product is porous biomass carbon, copper and volatile gases (hydrogen chloride and carbon dioxide). In addition, the yields of porous carbon after the activation process for JFC-0, JFC-6, JFC-8 and JFC-10 are 21%, 11.6%, 10% and 8.9%.
2.2. Materials characterization X-ray diffraction (XRD) pattern were performed using a Siemens D5000 X-ray diffractometer with nickel-filtered Cu K radiation. Raman spectra were carried out by a Renishaw inVia instrument. Thermal gravimetric analysis (TGA) was conducted with an ATGAQ50 in N2 atmosphere at a heating rate of 5 °C/min. The morphology of the samples was observed by scanning electron microscope (JEOL JSM7500F) and transmissions electron microscope (JEM-2100P).
3CuCl2 + C + 2H2 O → Cu + 2CuCl + CO2 + 4HCl
(1)
4CuCl + C + 2H2O → 4Cu + CO2 + 4HCl
(2)
The TGA weight-loss curves of raw jute fiber and the mixture of 2
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graphene layers in the (002) crystal plane, leading to the d-spacing between graphene decreases [23,31]. The results of XRD patterns show that the amount of the CuCl2 has no influence of the crystal structure. However, it can change the disorder degree of carbon material as Raman spectra shown in the Fig. 3b [31]. The D-band appearing at 1330 cm−1 is ascribed to the sp3 hybridized carbon with disordered state, while the peak of G-band near 1590 cm−1 corresponds to sp2 hybridized carbon with graphite structure. The ID/IG values of JFC-0, JFC-6, JFC-8 and JFC-10 sample are 1.07, 1.15, 1.28 and 1.12. JFC-0 has the lowest ID/IG value, indicating that more defects generated during the etching of CuCl2. The specific surface areas and pore-size distributions of the four samples are characterized through N2 adsorption-desorption measurement. Based on results in Fig. 4a, the isotherm of the four samples displays type I isotherm and has a steep increase of nitrogen adsorption amounts at a low relative pressure, indicating existence of plenty of micropores [32]. Besides, there are hysteresis loops of H4 in the relative pressure region of 0.5–1.0, indicating the existence of slit-shaped pores and mesopores, which occur during the etching of CuCl2 in the carbonization and activation process. The specific surface area of nonactivated jute fiber carbon (JFC-0) is 130.603 m2 g−1, whereas that of the JFC-6, JFC-8 and JFC-10 samples exhibit relatively high, which are 1432.17, 2043.528 and 1704.55 m2 g−1 due to their micropores and mesopores (Table 1). The large surface area and its suitable pore size distribution could facilitate good contact of JFC with electrolyte. Fig. 4b showed the BJH (Barrett-Joyner-Halenda) pore size distributions (PSDs) of the four samples. The average pore sizes of JFC-0, JFC-6, JFC8 and JFC-10 samples were 4.029, 4.833 3.594 and 3.093 nm (Table 1). JFC-8 sample is mainly composed of micropores between 1 and 2 nm and small mesopores around 3–4 nm. The Table 1 displays the total pore volumes of four samples are 0.132, 0.837, 1.109 and 0.969 cm3 g−1. In conclusion, the BJH adsorption and desorption measurements indicated the highly porous carbon material derived from jute fiber was because of activation CuCl2. Owing to its large surface area with hierarchical porosity, fast electrolyte transportation is achieved. It therefore demonstrates that the porous structure can be adjusted simply by changing the mass ratio of precursors. To further examine this carbonaceous material, the morphology and structure of product were investigated. The morphologies of the four samples show that the surface of carbon becomes rough through the etching with CuCl2. Obviously, there are some macropores can be seen in Fig. 5b, c and d, which serve as an ion-buffering reservoir [33]. With the increase of CuCl2, the amount of pores and the degree of surface irregularities are significantly increasing. Especially, when the amount of CuCl2 is 1:8, the presence of micropores, mesopores and macropores is responsible for the observed high specific capacity because of the promotion of the diffusion of ions and the transformation of electrolyte [34,35,36]. However, the amount of 1:6 or even less is not sufficient to etch the inside of jute fiber and to form plenty of pore structures. As for JFC-10, because of the high proportion of CuCl2, some structure
Fig. 2. Thermal gravimetric analysis (TGA) in N2 atmosphere of jute fiber and CuCl2.
CuCl2 sample are showed in Fig. 2. As for jute fiber, the thermal decomposition process has two stages: the first weight loss step from 250 to 300 °C is related with the dehydration of carbon precursor and the thermal decomposition of cellulose [25], the second stage at 310–450 °C is associated with volatilization of cellulosic fractions of the jute fiber [26]. As can be seen in the curves of jute fiber/CuCl2, the weight loss from 30 °C to 110 °C is due to the deduction of unbound water in the CuCl2 and jute fiber. The second weight-loss step at 110–450 °C includes the deduction of CuCl2 and the decomposition of carbon material [27]. The weight loss increases at the temperatures around 450–700 °C, which is ascribed to the faster reaction between CuCl2 and jute fiber showed in Eqs. (1) and (2). This is probably because the chemical activating agent CuCl2 begins to melt and the active pyrolysis reactions are becoming faster than before. Therefore, porous structure can become open and abundant. This is also why the amount of residual product of jute fiber/CuCl2 is far less than that of jute fiber. The total weight losses of untreated and treated jute fiber are about 80% and 97%, respectively. During the next stage at 700–800 °C, the weight loss is quite small and the activated carbon is already formed. Fig. 3a shows the XRD patterns of the JFC-0, JFC-6, JFC-8 and JFC10 samples. Clearly, all samples have two broad peaks appearing around 23°and 43°corresponding to (002) and (100) planes of amorphous carbon. It confirms that they have a disordered structure [28]. The weak (002) peak indicates low graphitization degree and disordered arrangement of carbon layers [29]. The (100) peak indicates that the presence of honeycomb structure formed by sp2 hybridized carbons [30]. There is a slightly shift to the right of the diffraction peak (002) for JFC-8, and it may be due to the dense parallel stacking of
Fig. 3. (a) XRD patterns and (b) Raman spectrum of the JFC-0, JFC-6, JFC-8 and JFC-10 samples. 3
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Fig. 4. (a) Nitrogen adsorption-desorption isotherms and (b) pore sizes distribution of JFC-0, JFC-6, JFC-8 and JFC-10 samples.
insertion and extraction, giving clearly better electrochemical performance than the untreated samples. Fig. 6b shows micropores (less than 2 nm) and mesopores (3–6 nm) are homogeneously distributed when the condition of ratio with 1:6. As for JFC-10 shown in Fig. 6d, there are also some micropores and mesopores. It appears that using CuCl2 as activating agent, an increase in the further ratio from 1:0 to 1:10 leads to an increase in the amount of micropores and the specific surface area, which is consistent with the N2 adsorption-desorption measurement. In addition, to investigate the porous structure of JFC-8 carbon, high-resolution transmission electron microscopy (HRTEM) pictures were displayed. It was obvious that porous and disordered carbon structures with wormhole-like micropores [37]. There are some micropores inside of the mesopores, which lead to good electrochemical properties. To evaluate the lithium storage properties of the carbonaceous material, a series of electrochemical measurements were performed. The charge-discharge profiles of the samples at a current density of 0.2C are showed in Fig. 7. In the first cycle, the discharge capacity of JFC, JFC-6, JFC-8 and JFC-10 samples are 763.9, 1036.3, 1794.6 and 1516 mA h g−1. The high initial discharging capacity of the JFC-8 sample could be attributed to a higher specific area resulting from the porous structure through activating by CuCl2. However, the irreversible capacity of JFC-8 was large which is 1095.9 mA h g−1 during the first
Table 1 Porosity parameters of prepared samples. Sample
JFC-0 JFC-6 JFC-8 JFC-10
Specific surface area (m2 g−1) 130.60 1432.17 2043.53 1704.55
Total pore volume (cm3 g−1) 0.132 0.837 1.109 0.969
Average pore size (nm) 4.029 4.833 3.594 3.093
collapse and more micropores have formed. Compared with JFC-6 and JFC-10 samples, JFC-8 sample has the best porous structure which has plentiful pores and some cracks. The porous structure may accelerate the electron transportation and maximize the electroactive surface area [34]. All above, the advantage of CuCl2 to the jute fiber carbon surface is to cause porous structure which is essential for electrode applications. The microstructures of the samples were also analyzed by transmission electron microscopy (TEM). As can be seen, the surface of JFC-0 sample is smooth (Fig. 6a) and there are a great number of micropores and some mesopores of the JFC-8 sample (Fig. 6c red rows). It is important to mention that the addition of CuCl2 at 1:8 contributes to the formation of quantities of micropores, mesopores and macropores. The existence of these pore structures provide active sites for lithium ion to
Fig. 5. SEM images of (a) JFC-0 (b) JFC-6 (c) JFC-8 and (d) JFC-10 samples. 4
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Fig. 6. TEM images of (a) JFC-0 (b) JFC-6 (c) JFC-8 and (d) JFC-10 samples and HRTEM images (e and f) of JFC-8.
special positions in the carbon material [38]. As the SEI layer prevents the electrolyte from decomposing, the reversible capacity becomes stable after the first cycle. As a result, coulomb efficiencies are becoming consistent and more than 90% in the subsequent process, indicating the stable electrochemical performance.
cycle. There are some reasons accounting for this phenomenon: (i) It becomes an active lithium storage host as a carbon electrode from its pristine form; (ii) A solid electrolyte interface (SEI) film is formed during the catalytic reduction of the electrolyte components on the active electrode; (iii) There is some irreversible lithium inserting into
Fig. 7. Charge-discharged profiles of (a) JFC-0 (b) JFC-6 (c) JFC-8 and (d) JFC-10 samples. 5
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Fig. 8. (a) Charge-discharge cycling performance of JFC-0, JFC-6, JFC-8 and JFC-10 samples (b) rate performance of four samples at 0.2C, 0.5C, 1C, 2C, 5C and back to 0.2C (c) charge-discharge cycling performance of JFC-0 and JFC-8 samples at 1C after 100 cycles.
Fig. 9. Cyclic voltammogram profiles of JFC-8 sample and the impedance curves of JFC-0, JFC-6, JFC-8 and JFC-10 samples.
increasing the contact area of electrode/electrolyte interface. Accordingly, the transmission distance of lithium ions shortens and specific capacity increases [40]. In addition, we can notice that at the higher current density (2C and 5C), JFC-8 sample exhibits similar capacity as the other samples, which may be due to the majority of the micropores and minority of mesopores. Mircopores can serve as charge accommodation which is essential for energy storage and mesopores can accelerate the process of ion diffusion and improve the power density. Thus, the amount of mesopores is not sufficient enough so that the capacity is relatively low at high current density [41]. When tested at higher rate 1C, the cycling performance of JFC-0 and JFC-8 is comparative (Fig. 8c), being as high as 246 mA h g−1 and 320 mA h g−1 respectively after 100 cycles. It is consistent with Fig. 8b that the JFC-8 sample has higher charge-discharge capacity than JFC-0 sample at 1C, which is due to its porous-structure. The Li-ion storage behavior of JFC-8 was investigated by Cyclic Voltammetry (CV) in Figs. 9a and 10. It is typical for carbonaceous
Fig. 8a shows the cycling performance curves of four samples at 0.2C. The discharge capacity of the JFC-0, JFC-6, JFC-8 and JFC-10 samples are 368 mA h g−1, 485 mA h g−1, 580.7 mA h g−1 and 423.6 mA h g−1 after 100 cycles, respectively. Clearly, the JFC-0 sample exhibits lower specific capacities than the others, indicating the porous structure carbon activated by CuCl2 has better charge and discharge performance. Since JFC-8 has larger pore volume, more surface vacancies and larger specific surface area, its reversible capacity is the highest, which is also attributed to the existence of pores providing positive lithium ion transfer kinetics [39]. Fig. 8b displays the capacities at different current densities at 0.2C, 0.5C, 1C, 5C and 0.2C. When the current densities return to 0.2C, the discharge capacities of all samples are restored, indicating the materials have outstanding rate performance. Meanwhile, the JFC-8 sample has higher charge-discharge capacity than other samples at 0.2C, 0.5C and 1C. The reason why it has suitable electrochemical properties is that the etching on the carbon by CuCl2 promotes porous structures and surface defects, 6
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Fig. 10. Kinetic analysis of the JFC-8 materials electrode at 1C after 100 cycles (a) CV profile at various scan rates; (b) Log(scan rate)- log (current) profile; (c) separation of the capacity and diffusion-controlled charge contributions; (d) Contribution ratio of capacitive and diffusion controlled behaviors at various scan rates.
be 0.83 (as shown in Fig. 10b) in the range of 0.5–1, which indicates it behaves as both battery and pseudocapacitance property [47]. Furthermore, through the Eqs. (5) and (6), the contribution of pseudocapacitance at 0.8 mV/s can be calculated at a specified potential V as shown in the Fig. 10c. At each specific voltage, k1v represents the contribution of the pseudocapacitance to the current. The results of contribution to the current at various scan rates are displayed in Fig. 10d [48]. The proportion of the capacitance at the low scan rate of 0.2 mV/s is about 48.4%, and gradually increases to 67.7% at 1 mV/s, which clearly present that the porous structures could result in the fast charge transfer [49].
anode materials. In the cathodic scan, there are two reduction peaks at around 0.75 and 1.5 V in the first cycle. The reduction peak at around 0.75 V is related to the SEI films caused by electrolyte decomposition on the surface of active electrode. The disappearance of this peak and no oxidation peak corresponding to it show that a stable SEI film is formed. The reduction peak around 1.5 V is owing to the irreversible reactions between lithium ions and functional group of carbon [42]. Besides, there are some reduction peaks at around 0.25 V, which may result from the adsorption process of lithium ion with the micro/mesopores carbon [31]. Further, the oxidation peak occurs between 0 and 0.5 V, which is ascribed to the deintercalation of lithium ion from graphite layers and the desorption of lithium ion from micropores or cavities of carbonaceous materials [43,44]. In addition, the curves of the next two cycles almost coincide, demonstrating the stable electrochemical properties. To further understand the electrochemical performance of the JFCs, the EIS measurement was taken before discharged. In the Fig. 9b, the semicircles in high frequency range are related with the charge transfer resistance [44]. For comparison, the diameter of semicircle for the JFC8 sample is the smallest in four samples. Theoretically, the charge transfer resistance of the JFC-8 is lower than that of the others because of its interior porous-structure provide more sites for electron to transfer. Furthermore, the inclined line at the low frequency region indicates the diffusion of lithium ions into carbon materials [45,46]. For comparison, the slopes of the straight line of other samples are all higher than the JFC-0. This phenomenon indicates that other samples with abundant pores have better diffusion of lithium ions. Porous jute fiber carbon which is treated with CuCl2 has more pores and bigger surface area, shortening the transmission distance of lithium ions, thus promoting the diffusion of lithium ions. The EIS results indicate JFC-8 sample has better electronic conductivity than JFC-0, JFC-6 and JFC10. To get more details about capacitance behavior and lithium storage of JFC-8, various scan rates of CV curves from 0.2 to 1.0 mv/s were displayed in the Fig. 10a. According to the Eqs. (3) and (4), v and i represent the scan rate and peak current, and the value b indicates the charge storage kinetics within the electrode. The b value is calculated to
i = a vb
(3)
log (i) = b log(v ) + log (a)
(4)
i (V) = k1 v + k2 v1/2
(5)
i (V)/ v1/2 = k1 v1/2 + k2
(6)
From the angle of material properties, jute fiber-derived biomass carbon in this work has its unique porous-structure that enables promising electrochemical performance (as shown in Table 2). Porous biomass carbon exhibits positive electrochemical performance, which is better than that of some reported biomass-based carbon anode materials. In addition, more details about lithium-storage mechanism are in Fig. 11.The porous structure of the obtained material is of great significance for the storage of lithium due to the adsorption sites for PF6−. Owing to the slow diffusion of lithium ions in the solid state, most lithium ions accumulate on the interface of the electrode particles and electrolyte. Hence, the existence of pores can provide more pathways for lithium ions to permeate from the electrolyte to the solid electrolyte. Besides, the large surface area increases the active electrode/electrolyte contact area, accelerating mass diffusion. There are some macropores on the surface of carbon block due to the etching effect of CuCl2 playing the role in transporting channels for electrolyte and lithium ion diffusion. Besides, the micropores which form on the carbon block during the carbonization and activation processes can act as deep trap sites for lithium storage and thus improving the capacity of lithium ion storage. 7
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Table 2 A comparison of the electrochemical properties of lithium ion batteries used JFC and those of some other biomass-based carbon materials as anodes. Samples
Carbon sources
Initial reversible capacity (mAh/g)
Cyclability (mAh/g)
Potential range (V)
Ref.
Porous biomass carbon Hierarchical porous carbon Carbonaceous material Biomass carbon Activated carbon Microporous carbon Activated carbon Carbon fibers Disordered carbonaceous materials Disordered carbonaceous materials
Jute fiber Rice straw Spongy pomelo peels Ramie fibers Sisal fiber Pinecone hull Sisal fiber Rice husk Banana fibers Coffee shell
699 986 450 432 646 321 350 403 401 456
581 257 452 523 250 350 300 396 – –
0.01–3 0.005–3 0.02–3 0.01–3 0.01–3 0.02–2 0.02–3 – 0.02–2.5 0.002–2.5
This work [50] [30] [51] [13] [52] [10] [3] [53] [54]
at at at at at at at at at at
0.2C 0.1C 40 mA/g 100 mA/g 0.1C 10 mA/g 0.1C 0.2C 0.1C 0.2C
at at at at at at at at
0.2C 2C 90 mA/g 100 mA/g 0.1C 10 mA/g 0.1C 75 mA/g
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Fig. 11. Schematic representation of the lithium ion storage mechanism.
Mesopores provide ion-highways for ion transmission [35,36,50]. All these factors lead to the lithium storage on the jute fiber based porous carbon electrode.
4. Conclusions In summary, a porous-structure carbon material with a high specific surface area (2043.528 m2 g−1) was synthesized from jute fiber via a facile and economic method. Through activating by CuCl2, abundant nanopores including micropores, mesopores and macropores were obtained. JFC-8 was used as anodes in lithium ion battery and had a high specific capacity (the reversible capacity is 580.4 mA h g−1 at a current density of 0.2C), excellent stability and superior rate performance. This treatment method can be widely used in biomass carbons especially in natural fibers, not only applying in energy storage but also in catalysis, adsorption and other fields.
Acknowledgment This work was financially supported by National Key Research and Development Program of China (2016YFF0201204); the China Postdoctoral Science Foundation (2017M611321); the Project of Jilin Provincial Science and Technology Department (20180201074GX, 20190201110JC); the Project of Jilin Provincial Education Department (JJKH20180130KJ); Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University (2019-8).
Appendix A. Supplementary data Supplementary data to this article can be found online at https:// doi.org/10.1016/j.diamond.2019.107514. 8
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Biomass porous carbon derived from jute fiber as anode materials for lithium-ion batteries ⁎
Yanli Doua, Xin Liua, Kaifeng Yua, Xiaofeng Wangb, Weiping Liuc, Jicai Lianga,d, , Ce Lianga,
T ⁎⁎
a
Key Laboratory of Automobile Materials, Ministry of Education, College of Materials Science and Engineering, Jilin University, Changchun 130025, China State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130025, Jilin, China c College of Instrumentation and Electrical Engineering, Jilin University, Changchun 130025, Jilin, China d Roll Forging Research Institute, Jilin University, Changchun 130025, Jilin, China b
A R T I C LE I N FO
A B S T R A C T
Keywords: Jute fiber Biomass Porous carbon Anode Lithium-ion battery
Porous carbon derived from jute fiber through a convenient approach has been explored as an anode for lithiumion batteries. High BET surface area of 2043.528 m2 g−1 and porous structure of carbon is obtained by CuCl2 activation. The resulting carbonaceous material exhibits excellent specific charge capacity as high as 580.4 mA h g−1 at the current density of 0.2C after 100 cycles. This research can provide a novel route for the production of high performance energy storage materials from biomass wastes.
1. Introduction With the consumption of fossil fuel and global warming, concerns of the energy and environment have increased in recent years. Meanwhile, population and economic growth are leading to the increasing need of energy storage [1,2]. It is well known that lithium-based technology is the most promising storage system as of today. Lithium ion batteries (LIBs) are widely used by portable electronic devices and electric vehicles (EVs) in people's life [3] due to its high energy density, long cycle life and light weight. Generally, graphite is the most popular anode material for LIBs because of its high density, promising electrical conductivity and excellent cycle stability [4]. However, the limited capacity of graphite carbon used for the anode materials in lithium batteries is only 372 mA h g−1 [5]. Due to its limited specific capacity, new carbon materials should be developed for high performance electrode. Besides, considering the environmental issue and economic cost, ideal electrode materials should be derived from renewable resources. To prepare superior electrode material, activated carbon from biomass such as bamboo wood, bamboo char, microalgae, rice husk and peanut skin were used as precursor materials [6–12]. Yu et al. [13] used sisal fibers to prepare activated carbon anode for lithium-ion batteries, which possessed insertion capacity of 646 mA h g−1 from the first cycle at 0.1 C, but exhibited initial coulombic efficiencies of only 41%. The results of these reports give clear support for the lignocellulosic natural
fibers (including sisal fiber, jute fiber and hemp fiber) to make into activated carbon as anode materials. Jute fiber is a kind of biomass extracted from the stem or bast of genus corchorus [14]. The world annual production of the jute is 3600 thousand tones [13]. It is one of the cheapest natural fibers in the world. These kind of natural fibers are made up of crystalline microfibrils based on cellulose (58–63%), which are connected by amorphous lignin (12–15%) and hemicelluloses (20–22%) [15,16]. In the jute fiber, the molecules are highly oriented parallel in the fibrils which are connected with other fibrils. As mentioned before, jute fiber is a carbon source which is low-cost, readily available, widely distributed, environmentally friendly and renewable. Therefore, jute fibers have been chosen to develop for new carbonbased anode materials with high lithium ion storage capacity in our work. As of today, the main methods to make porous structures in carbon includes the activation method [17], template method [18,19], organic gel carbonization method [20] and blend polymer carbonization method [21]. In the chemical method, the CuCl2 activation method is considered to be an effective route for preparing a high specific surface area porous carbon [22,23]. In this study, CuCl2 were used as activation agent based on the following reasons. Firstly, conversion of jute fiber precursors into porous structure carbon occurs during the heatment process of the mixture of CuCl2 and jute fiber after grinding them into powder. Furthermore, porous nature and high surface area of jute fiber
⁎
Correspondence to: J. Liang, Key Laboratory of Automobile Materials, Ministry of Education, College of Materials Science and Engineering, Jilin University, Changchun 130025, China. ⁎⁎ Corresponding author. E-mail addresses: [email protected] (J. Liang), [email protected] (C. Liang). https://doi.org/10.1016/j.diamond.2019.107514 Received 30 April 2019; Received in revised form 3 August 2019; Accepted 12 August 2019 Available online 14 August 2019 0925-9635/ © 2019 Elsevier B.V. All rights reserved.
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Fig. 1. The formation process of porous carbon derived from jute fibers.
Brunauer–Emmett–Teller analysis was performed on Micrometrics ASAP 2420 surface analyzer to obtain specific surface area and pore size distribution of different samples.
carbon have been obtained. In addition, the size and distribution of the pores could be adjusted by the amount of activation agent CuCl2. Beyond characterization of pores size and microstructure, jute fiber carbon was demonstrated to be employed as electrode material with excellent reversible capacity and rate capability. Finally, this method has a hopeful prospect due to its feature of straightforward and cheapness. Therefore, in this study, CuCl2 were used as activation agent based on the above reasons. Firstly, conversion of jute fiber precursors into porous structure carbon occurs during the heating process of the mixture of CuCl2 and jute fiber after grinding them into powder. Furthermore, porous nature and high surface area of jute fiber carbon have been obtained. In addition, the size and distribution of the pores could be adjusted by the amount of activation agent CuCl2. Beyond characterization of pores size and microstructure, jute fiber carbon was demonstrated to be employed as electrode material with excellent reversible capacity and rate capability. Finally, this method has a hopeful prospect due to its feature of straightforward and cheapness.
2.3. Electrochemical measurements Electrochemical property was tested using coin cells (CR2025, half cell) which were assembled in Ar-filled glovebox with moisture and oxygen concentrations below 1 ppm. The carbon electrode was made by coating the slurry of active substance, acetylene black and polyvinyl fluoride (PVDF) at the mass ratio of 8:1:1 dissolved in N-methyl-2pyrrolidone (NMP) on a copper foil and dried in a vacuum oven at 120 °C for 12 h. The electrolyte was 1 mol L−1 LiPF6 in a 50: 50 w/w mixture of ethylene carbonate and diethyl carbonate. The cyclic voltammetry curve and impedance curve were performed on a CHI660C electrochemical workstation. The CV measurements were tested between 0 and 3.0 V at a scan rate of 0.1 mV/s. The EIS measurements were analyzed in the range of 100 kHz to 10 m Hz. The charge–discharge performance were tested between 0.02 V and 3.0 V at a 0.2C (1C = 372 mA/g) rate on a LAND (CT2001A) battery test system.
2. Experimental 2.1. Materials synthesis
3. Results and discussion Jute fibers were washed with deionized water to remove the impurities. And they were cut into small pieces around 3 mm long and mixed with copper chloride at the weight ratio of 1:0, 1:6, 1:8 and 1:10. After fully impregnation by stirring for 12 h and being ultrasonic for 8 h, the samples were dried in the oven at 80 °C. Then they were ground fully in an agate mortar and put in the porcelain boat.(as shown in Fig. S1) The activation process was carried out through heating in the tube furnace at 800 °C for 2 h under argon atmosphere with the heating rate of 2 °C/min. When cooled to room temperature, samples were grinded fully in an agate mortar and washed with 2 M hydrochloric acid solution until the red matter disappeared. After washing to neutral with deionized water, jute fiber activated carbons were denoted as JFC-0, JFC-6, JFC-8 and JFC-10.
Fig. 1 illustrates the material synthesis process applied to the electrodes. Jute fiber has natural fibrous structure providing stacked capillaries to absorb CuCl2, leading to a uniform mixture of them. In the process of activation, CuCl2 is used as activating agent to fulfill the carbonization process according to the Eqs. (1) and (2) [22,24]. It is proved that the X-ray diffraction (XRD) tests on the unwashed resulted product under 800 °C/2 h (Fig. S2.a) and 500 °C/1 h (Fig. S2.b) show the presence of Cu (Fig. S2.a) and CuCl (Fig. S2.b) in the composite. The reactions proceeded with jute fiber carbon and CuCl2 include some simultaneous and continuous reactions. In this process, copper, cuprous chloride and some gases such as carbon dioxide and hydrogen chloride are generated, and pores are formed because of the corrosion on surface. Besides, the further reaction occurs between the intermediate product cuprous chloride and jute fiber carbon, forming more interior pores. As a consequence, the final product is porous biomass carbon, copper and volatile gases (hydrogen chloride and carbon dioxide). In addition, the yields of porous carbon after the activation process for JFC-0, JFC-6, JFC-8 and JFC-10 are 21%, 11.6%, 10% and 8.9%.
2.2. Materials characterization X-ray diffraction (XRD) pattern were performed using a Siemens D5000 X-ray diffractometer with nickel-filtered Cu K radiation. Raman spectra were carried out by a Renishaw inVia instrument. Thermal gravimetric analysis (TGA) was conducted with an ATGAQ50 in N2 atmosphere at a heating rate of 5 °C/min. The morphology of the samples was observed by scanning electron microscope (JEOL JSM7500F) and transmissions electron microscope (JEM-2100P).
3CuCl2 + C + 2H2 O → Cu + 2CuCl + CO2 + 4HCl
(1)
4CuCl + C + 2H2O → 4Cu + CO2 + 4HCl
(2)
The TGA weight-loss curves of raw jute fiber and the mixture of 2
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graphene layers in the (002) crystal plane, leading to the d-spacing between graphene decreases [23,31]. The results of XRD patterns show that the amount of the CuCl2 has no influence of the crystal structure. However, it can change the disorder degree of carbon material as Raman spectra shown in the Fig. 3b [31]. The D-band appearing at 1330 cm−1 is ascribed to the sp3 hybridized carbon with disordered state, while the peak of G-band near 1590 cm−1 corresponds to sp2 hybridized carbon with graphite structure. The ID/IG values of JFC-0, JFC-6, JFC-8 and JFC-10 sample are 1.07, 1.15, 1.28 and 1.12. JFC-0 has the lowest ID/IG value, indicating that more defects generated during the etching of CuCl2. The specific surface areas and pore-size distributions of the four samples are characterized through N2 adsorption-desorption measurement. Based on results in Fig. 4a, the isotherm of the four samples displays type I isotherm and has a steep increase of nitrogen adsorption amounts at a low relative pressure, indicating existence of plenty of micropores [32]. Besides, there are hysteresis loops of H4 in the relative pressure region of 0.5–1.0, indicating the existence of slit-shaped pores and mesopores, which occur during the etching of CuCl2 in the carbonization and activation process. The specific surface area of nonactivated jute fiber carbon (JFC-0) is 130.603 m2 g−1, whereas that of the JFC-6, JFC-8 and JFC-10 samples exhibit relatively high, which are 1432.17, 2043.528 and 1704.55 m2 g−1 due to their micropores and mesopores (Table 1). The large surface area and its suitable pore size distribution could facilitate good contact of JFC with electrolyte. Fig. 4b showed the BJH (Barrett-Joyner-Halenda) pore size distributions (PSDs) of the four samples. The average pore sizes of JFC-0, JFC-6, JFC8 and JFC-10 samples were 4.029, 4.833 3.594 and 3.093 nm (Table 1). JFC-8 sample is mainly composed of micropores between 1 and 2 nm and small mesopores around 3–4 nm. The Table 1 displays the total pore volumes of four samples are 0.132, 0.837, 1.109 and 0.969 cm3 g−1. In conclusion, the BJH adsorption and desorption measurements indicated the highly porous carbon material derived from jute fiber was because of activation CuCl2. Owing to its large surface area with hierarchical porosity, fast electrolyte transportation is achieved. It therefore demonstrates that the porous structure can be adjusted simply by changing the mass ratio of precursors. To further examine this carbonaceous material, the morphology and structure of product were investigated. The morphologies of the four samples show that the surface of carbon becomes rough through the etching with CuCl2. Obviously, there are some macropores can be seen in Fig. 5b, c and d, which serve as an ion-buffering reservoir [33]. With the increase of CuCl2, the amount of pores and the degree of surface irregularities are significantly increasing. Especially, when the amount of CuCl2 is 1:8, the presence of micropores, mesopores and macropores is responsible for the observed high specific capacity because of the promotion of the diffusion of ions and the transformation of electrolyte [34,35,36]. However, the amount of 1:6 or even less is not sufficient to etch the inside of jute fiber and to form plenty of pore structures. As for JFC-10, because of the high proportion of CuCl2, some structure
Fig. 2. Thermal gravimetric analysis (TGA) in N2 atmosphere of jute fiber and CuCl2.
CuCl2 sample are showed in Fig. 2. As for jute fiber, the thermal decomposition process has two stages: the first weight loss step from 250 to 300 °C is related with the dehydration of carbon precursor and the thermal decomposition of cellulose [25], the second stage at 310–450 °C is associated with volatilization of cellulosic fractions of the jute fiber [26]. As can be seen in the curves of jute fiber/CuCl2, the weight loss from 30 °C to 110 °C is due to the deduction of unbound water in the CuCl2 and jute fiber. The second weight-loss step at 110–450 °C includes the deduction of CuCl2 and the decomposition of carbon material [27]. The weight loss increases at the temperatures around 450–700 °C, which is ascribed to the faster reaction between CuCl2 and jute fiber showed in Eqs. (1) and (2). This is probably because the chemical activating agent CuCl2 begins to melt and the active pyrolysis reactions are becoming faster than before. Therefore, porous structure can become open and abundant. This is also why the amount of residual product of jute fiber/CuCl2 is far less than that of jute fiber. The total weight losses of untreated and treated jute fiber are about 80% and 97%, respectively. During the next stage at 700–800 °C, the weight loss is quite small and the activated carbon is already formed. Fig. 3a shows the XRD patterns of the JFC-0, JFC-6, JFC-8 and JFC10 samples. Clearly, all samples have two broad peaks appearing around 23°and 43°corresponding to (002) and (100) planes of amorphous carbon. It confirms that they have a disordered structure [28]. The weak (002) peak indicates low graphitization degree and disordered arrangement of carbon layers [29]. The (100) peak indicates that the presence of honeycomb structure formed by sp2 hybridized carbons [30]. There is a slightly shift to the right of the diffraction peak (002) for JFC-8, and it may be due to the dense parallel stacking of
Fig. 3. (a) XRD patterns and (b) Raman spectrum of the JFC-0, JFC-6, JFC-8 and JFC-10 samples. 3
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Fig. 4. (a) Nitrogen adsorption-desorption isotherms and (b) pore sizes distribution of JFC-0, JFC-6, JFC-8 and JFC-10 samples.
insertion and extraction, giving clearly better electrochemical performance than the untreated samples. Fig. 6b shows micropores (less than 2 nm) and mesopores (3–6 nm) are homogeneously distributed when the condition of ratio with 1:6. As for JFC-10 shown in Fig. 6d, there are also some micropores and mesopores. It appears that using CuCl2 as activating agent, an increase in the further ratio from 1:0 to 1:10 leads to an increase in the amount of micropores and the specific surface area, which is consistent with the N2 adsorption-desorption measurement. In addition, to investigate the porous structure of JFC-8 carbon, high-resolution transmission electron microscopy (HRTEM) pictures were displayed. It was obvious that porous and disordered carbon structures with wormhole-like micropores [37]. There are some micropores inside of the mesopores, which lead to good electrochemical properties. To evaluate the lithium storage properties of the carbonaceous material, a series of electrochemical measurements were performed. The charge-discharge profiles of the samples at a current density of 0.2C are showed in Fig. 7. In the first cycle, the discharge capacity of JFC, JFC-6, JFC-8 and JFC-10 samples are 763.9, 1036.3, 1794.6 and 1516 mA h g−1. The high initial discharging capacity of the JFC-8 sample could be attributed to a higher specific area resulting from the porous structure through activating by CuCl2. However, the irreversible capacity of JFC-8 was large which is 1095.9 mA h g−1 during the first
Table 1 Porosity parameters of prepared samples. Sample
JFC-0 JFC-6 JFC-8 JFC-10
Specific surface area (m2 g−1) 130.60 1432.17 2043.53 1704.55
Total pore volume (cm3 g−1) 0.132 0.837 1.109 0.969
Average pore size (nm) 4.029 4.833 3.594 3.093
collapse and more micropores have formed. Compared with JFC-6 and JFC-10 samples, JFC-8 sample has the best porous structure which has plentiful pores and some cracks. The porous structure may accelerate the electron transportation and maximize the electroactive surface area [34]. All above, the advantage of CuCl2 to the jute fiber carbon surface is to cause porous structure which is essential for electrode applications. The microstructures of the samples were also analyzed by transmission electron microscopy (TEM). As can be seen, the surface of JFC-0 sample is smooth (Fig. 6a) and there are a great number of micropores and some mesopores of the JFC-8 sample (Fig. 6c red rows). It is important to mention that the addition of CuCl2 at 1:8 contributes to the formation of quantities of micropores, mesopores and macropores. The existence of these pore structures provide active sites for lithium ion to
Fig. 5. SEM images of (a) JFC-0 (b) JFC-6 (c) JFC-8 and (d) JFC-10 samples. 4
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Fig. 6. TEM images of (a) JFC-0 (b) JFC-6 (c) JFC-8 and (d) JFC-10 samples and HRTEM images (e and f) of JFC-8.
special positions in the carbon material [38]. As the SEI layer prevents the electrolyte from decomposing, the reversible capacity becomes stable after the first cycle. As a result, coulomb efficiencies are becoming consistent and more than 90% in the subsequent process, indicating the stable electrochemical performance.
cycle. There are some reasons accounting for this phenomenon: (i) It becomes an active lithium storage host as a carbon electrode from its pristine form; (ii) A solid electrolyte interface (SEI) film is formed during the catalytic reduction of the electrolyte components on the active electrode; (iii) There is some irreversible lithium inserting into
Fig. 7. Charge-discharged profiles of (a) JFC-0 (b) JFC-6 (c) JFC-8 and (d) JFC-10 samples. 5
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Fig. 8. (a) Charge-discharge cycling performance of JFC-0, JFC-6, JFC-8 and JFC-10 samples (b) rate performance of four samples at 0.2C, 0.5C, 1C, 2C, 5C and back to 0.2C (c) charge-discharge cycling performance of JFC-0 and JFC-8 samples at 1C after 100 cycles.
Fig. 9. Cyclic voltammogram profiles of JFC-8 sample and the impedance curves of JFC-0, JFC-6, JFC-8 and JFC-10 samples.
increasing the contact area of electrode/electrolyte interface. Accordingly, the transmission distance of lithium ions shortens and specific capacity increases [40]. In addition, we can notice that at the higher current density (2C and 5C), JFC-8 sample exhibits similar capacity as the other samples, which may be due to the majority of the micropores and minority of mesopores. Mircopores can serve as charge accommodation which is essential for energy storage and mesopores can accelerate the process of ion diffusion and improve the power density. Thus, the amount of mesopores is not sufficient enough so that the capacity is relatively low at high current density [41]. When tested at higher rate 1C, the cycling performance of JFC-0 and JFC-8 is comparative (Fig. 8c), being as high as 246 mA h g−1 and 320 mA h g−1 respectively after 100 cycles. It is consistent with Fig. 8b that the JFC-8 sample has higher charge-discharge capacity than JFC-0 sample at 1C, which is due to its porous-structure. The Li-ion storage behavior of JFC-8 was investigated by Cyclic Voltammetry (CV) in Figs. 9a and 10. It is typical for carbonaceous
Fig. 8a shows the cycling performance curves of four samples at 0.2C. The discharge capacity of the JFC-0, JFC-6, JFC-8 and JFC-10 samples are 368 mA h g−1, 485 mA h g−1, 580.7 mA h g−1 and 423.6 mA h g−1 after 100 cycles, respectively. Clearly, the JFC-0 sample exhibits lower specific capacities than the others, indicating the porous structure carbon activated by CuCl2 has better charge and discharge performance. Since JFC-8 has larger pore volume, more surface vacancies and larger specific surface area, its reversible capacity is the highest, which is also attributed to the existence of pores providing positive lithium ion transfer kinetics [39]. Fig. 8b displays the capacities at different current densities at 0.2C, 0.5C, 1C, 5C and 0.2C. When the current densities return to 0.2C, the discharge capacities of all samples are restored, indicating the materials have outstanding rate performance. Meanwhile, the JFC-8 sample has higher charge-discharge capacity than other samples at 0.2C, 0.5C and 1C. The reason why it has suitable electrochemical properties is that the etching on the carbon by CuCl2 promotes porous structures and surface defects, 6
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Fig. 10. Kinetic analysis of the JFC-8 materials electrode at 1C after 100 cycles (a) CV profile at various scan rates; (b) Log(scan rate)- log (current) profile; (c) separation of the capacity and diffusion-controlled charge contributions; (d) Contribution ratio of capacitive and diffusion controlled behaviors at various scan rates.
be 0.83 (as shown in Fig. 10b) in the range of 0.5–1, which indicates it behaves as both battery and pseudocapacitance property [47]. Furthermore, through the Eqs. (5) and (6), the contribution of pseudocapacitance at 0.8 mV/s can be calculated at a specified potential V as shown in the Fig. 10c. At each specific voltage, k1v represents the contribution of the pseudocapacitance to the current. The results of contribution to the current at various scan rates are displayed in Fig. 10d [48]. The proportion of the capacitance at the low scan rate of 0.2 mV/s is about 48.4%, and gradually increases to 67.7% at 1 mV/s, which clearly present that the porous structures could result in the fast charge transfer [49].
anode materials. In the cathodic scan, there are two reduction peaks at around 0.75 and 1.5 V in the first cycle. The reduction peak at around 0.75 V is related to the SEI films caused by electrolyte decomposition on the surface of active electrode. The disappearance of this peak and no oxidation peak corresponding to it show that a stable SEI film is formed. The reduction peak around 1.5 V is owing to the irreversible reactions between lithium ions and functional group of carbon [42]. Besides, there are some reduction peaks at around 0.25 V, which may result from the adsorption process of lithium ion with the micro/mesopores carbon [31]. Further, the oxidation peak occurs between 0 and 0.5 V, which is ascribed to the deintercalation of lithium ion from graphite layers and the desorption of lithium ion from micropores or cavities of carbonaceous materials [43,44]. In addition, the curves of the next two cycles almost coincide, demonstrating the stable electrochemical properties. To further understand the electrochemical performance of the JFCs, the EIS measurement was taken before discharged. In the Fig. 9b, the semicircles in high frequency range are related with the charge transfer resistance [44]. For comparison, the diameter of semicircle for the JFC8 sample is the smallest in four samples. Theoretically, the charge transfer resistance of the JFC-8 is lower than that of the others because of its interior porous-structure provide more sites for electron to transfer. Furthermore, the inclined line at the low frequency region indicates the diffusion of lithium ions into carbon materials [45,46]. For comparison, the slopes of the straight line of other samples are all higher than the JFC-0. This phenomenon indicates that other samples with abundant pores have better diffusion of lithium ions. Porous jute fiber carbon which is treated with CuCl2 has more pores and bigger surface area, shortening the transmission distance of lithium ions, thus promoting the diffusion of lithium ions. The EIS results indicate JFC-8 sample has better electronic conductivity than JFC-0, JFC-6 and JFC10. To get more details about capacitance behavior and lithium storage of JFC-8, various scan rates of CV curves from 0.2 to 1.0 mv/s were displayed in the Fig. 10a. According to the Eqs. (3) and (4), v and i represent the scan rate and peak current, and the value b indicates the charge storage kinetics within the electrode. The b value is calculated to
i = a vb
(3)
log (i) = b log(v ) + log (a)
(4)
i (V) = k1 v + k2 v1/2
(5)
i (V)/ v1/2 = k1 v1/2 + k2
(6)
From the angle of material properties, jute fiber-derived biomass carbon in this work has its unique porous-structure that enables promising electrochemical performance (as shown in Table 2). Porous biomass carbon exhibits positive electrochemical performance, which is better than that of some reported biomass-based carbon anode materials. In addition, more details about lithium-storage mechanism are in Fig. 11.The porous structure of the obtained material is of great significance for the storage of lithium due to the adsorption sites for PF6−. Owing to the slow diffusion of lithium ions in the solid state, most lithium ions accumulate on the interface of the electrode particles and electrolyte. Hence, the existence of pores can provide more pathways for lithium ions to permeate from the electrolyte to the solid electrolyte. Besides, the large surface area increases the active electrode/electrolyte contact area, accelerating mass diffusion. There are some macropores on the surface of carbon block due to the etching effect of CuCl2 playing the role in transporting channels for electrolyte and lithium ion diffusion. Besides, the micropores which form on the carbon block during the carbonization and activation processes can act as deep trap sites for lithium storage and thus improving the capacity of lithium ion storage. 7
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Table 2 A comparison of the electrochemical properties of lithium ion batteries used JFC and those of some other biomass-based carbon materials as anodes. Samples
Carbon sources
Initial reversible capacity (mAh/g)
Cyclability (mAh/g)
Potential range (V)
Ref.
Porous biomass carbon Hierarchical porous carbon Carbonaceous material Biomass carbon Activated carbon Microporous carbon Activated carbon Carbon fibers Disordered carbonaceous materials Disordered carbonaceous materials
Jute fiber Rice straw Spongy pomelo peels Ramie fibers Sisal fiber Pinecone hull Sisal fiber Rice husk Banana fibers Coffee shell
699 986 450 432 646 321 350 403 401 456
581 257 452 523 250 350 300 396 – –
0.01–3 0.005–3 0.02–3 0.01–3 0.01–3 0.02–2 0.02–3 – 0.02–2.5 0.002–2.5
This work [50] [30] [51] [13] [52] [10] [3] [53] [54]
at at at at at at at at at at
0.2C 0.1C 40 mA/g 100 mA/g 0.1C 10 mA/g 0.1C 0.2C 0.1C 0.2C
at at at at at at at at
0.2C 2C 90 mA/g 100 mA/g 0.1C 10 mA/g 0.1C 75 mA/g
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Fig. 11. Schematic representation of the lithium ion storage mechanism.
Mesopores provide ion-highways for ion transmission [35,36,50]. All these factors lead to the lithium storage on the jute fiber based porous carbon electrode.
4. Conclusions In summary, a porous-structure carbon material with a high specific surface area (2043.528 m2 g−1) was synthesized from jute fiber via a facile and economic method. Through activating by CuCl2, abundant nanopores including micropores, mesopores and macropores were obtained. JFC-8 was used as anodes in lithium ion battery and had a high specific capacity (the reversible capacity is 580.4 mA h g−1 at a current density of 0.2C), excellent stability and superior rate performance. This treatment method can be widely used in biomass carbons especially in natural fibers, not only applying in energy storage but also in catalysis, adsorption and other fields.
Acknowledgment This work was financially supported by National Key Research and Development Program of China (2016YFF0201204); the China Postdoctoral Science Foundation (2017M611321); the Project of Jilin Provincial Science and Technology Department (20180201074GX, 20190201110JC); the Project of Jilin Provincial Education Department (JJKH20180130KJ); Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University (2019-8).
Appendix A. Supplementary data Supplementary data to this article can be found online at https:// doi.org/10.1016/j.diamond.2019.107514. 8
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