Biomass Based Materials

#### **Chapter 2**

## Biomass-Based Carbon Electrodes in the Design of Supercapacitors: An Electrochemical Point of View

*Antony Bazan-Aguilar, Elvis O. López, Miguel Ponce-Vargas and Angélica M. Baena-Moncada*

#### **Abstract**

The urgent demand of sustainable long-lasting batteries has fostered the improvement of extended-use technologies e.g., Li-ion batteries, as well as the development of alternative energy storage strategies like supercapacitors. In this context, new carbon-based materials were developed to attain higher electrochemical performances, even though several of these materials are not obtained by ecofriendly methods and/or in a considerable amount for practical purposes. However, up-to-date reports stand out the scopes achieved by biomass-based carbon materials as energy storage electrodes combining outstanding physicochemical and electrochemical properties with low-pollutant and low-cost production. On this basis, this chapter will expose several aspects of the synthesis of carbon-based electrodes from biomass, focusing on the influence of their surface properties: porosity, crystallinity, and morphology on their electrochemical performance in supercapacitors.

**Keywords:** Biomass-based carbon electrodes, Energy storage device, Surface properties, Electrochemical performance, Supercapacitors

#### **1. Introduction**

Nowadays, the search for new eco-friendly energy systems is a priority to mitigate the global impact associated with fossil fuel energy consumption [1–4]. At the same time, novel electronic devices need to be developed to produce more efficient energy storage systems with higher capacity and longer average lifetimes [5]. In this regard, electrical double layer capacitors (EDLC), pseudocapacitors [6] and flexible solid-state supercapacitors (FSSC) [7, 8], are able to cover the above-mentioned demands. Particularly, carbon-based capacitors exhibit significant advantages, such as high-power density, low weight and flexibility, in contrast to conventional graphite-based systems [9]. To achieve a better capacitance, electrodes based in porous carbon materials can be employed, given their interesting morphological features, like high specific surface area (*S*BET), defined-porosity, and hierarchical arrangement [10]. Recently, the use of biomass as precursor material has allowed the design of carbon-based energy storage systems with outstanding electrochemical and mechanical properties [11, 12].

The energy storage mechanism in these materials consists in the accumulation of electrostatic charges on their surface (**Figure 1**), [13] implying that, density of stored charges depends on the material morphology (roughness and pores), and the size of the

#### **Figure 1.**

*Schematic representation of a loaded EDLC supercapacitor and pore accessibility (inset) with respect to the electrolyte. Figure adapted from [13, 14].*

involved electrolyte ions [14]. **Figure 1** shows the interplay between electrode porosity and ion-electrolyte size for the electrostatic charge accumulation, in terms of pore accessibility. In this way, activated carbons mainly exhibit three pore sizes [15]: micro (< 2 nm), meso (2–50 nm) and macro (> 50 nm), being the micropores and mesopores the ones that most contribute to the increase of the capacitance [16]. Nevertheless, even though carbon-based materials have high surface areas (1000–2000 m2 g<sup>1</sup> ), they still have low specific capacitances due to their limited mesoporosity [14].

The carbons from biomass can be obtained from various natural sources, such as: garlic skin, bamboo, rice husk, eucalyptus-bark, lignin, cellulose, orange peel, etc. [6, 17–22], making biomass a sustainable source, also available in large quantities from industrial waste [18]. Furthermore, the carbons obtained from biomass present a diversified class of fibrous and porous structures [22], with capacitances ranging from 100 to 430 F g<sup>1</sup> [16, 23]. However, these values vary according to the carbon activation method, which is strongly related to the resulting electrode poresize. Such processes of carbon activation from biomass can be divided into two categories: i) physical activation and ii) chemical activation.

#### **1.1 Physical activation processes**

In this process the biomass undergoes a pyrolysis treatment at temperatures between 600 and 900°C in inert atmosphere. Then, the material is commonly exposed to an oxidizing atmosphere of CO2, carried out at temperatures between 600 and 1200°C. Yu et al. used this method to obtain activated carbon from cattail biomass [24], resulting in an activated carbon with a surface area of 441 m2 g<sup>1</sup> and a specific capacitance of 126 F g<sup>1</sup> (current density of 0.5 A g<sup>1</sup> in KOH 6 mol L<sup>1</sup> electrolyte) [18].

#### **1.2 Chemical activation processes**

In this process, the carbon precursor (biomass) is treated (soaked) with chemical activators, such as: KOH, NaOH, H3PO4, ZnCl2, H2SO4, among others. *Biomass-Based Carbon Electrodes in the Design of Supercapacitors: An Electrochemical… DOI: http://dx.doi.org/10.5772/intechopen.97649*

Subsequently, the biomass is carbonized at temperatures between 400 and 900°C [25]. During this activation, redox processes and substitution of large particles take place, leading to the desired high porosity. In addition, physical activation occurs due to the interaction of the reaction products such as: H2, H2O, CO and CO2. Remarkably, these molecules also contribute to the pore formation.

Using KOH as a chemical activator, K<sup>0</sup> (metallic) is produced which occupies interstitial positions in the carbon structure, inducing expansion in the material as well as producing a high microporosity. A proposed mechanism of the activation process using KOH is shown in the following redox reactions [26]:

$$\text{26KOH} + \text{2C} \rightarrow \text{2K} + \text{3H}\_2 + \text{2K}\_2\text{CO}\_3 \tag{1}$$

$$\text{2K}\_2\text{CO}\_3 \rightarrow \text{2K}\_2\text{O} + \text{2CO}\_2\tag{2}$$

$$\text{K}\_2\text{CO}\_3 + 2\text{C} \to 2\text{K} + \text{3CO} \tag{3}$$

$$\text{CO}\_2 + \text{C} \to \text{2CO} \tag{4}$$

$$\text{C} + \text{K}\_2\text{O} \rightarrow 2\text{K} + \text{CO} \tag{5}$$

Diverse works have used the chemical activation process from KOH, Barzegar et al. was one of them and produced mesoporous carbon from coconut shell, obtaining a specific surface area of 1416 m<sup>2</sup> g�<sup>1</sup> and a specific capacity of 186 F g�<sup>1</sup> [27]. Zhang et al. used bamboo to obtain mesoporous carbon from KOH as an activator. Zhang obtained a high specific surface area of 2221 m<sup>2</sup> g�<sup>1</sup> and a specific capacitance of 293 F g�<sup>1</sup> at 0.5 A g�<sup>1</sup> in KOH 3.0 mol L�<sup>1</sup> [18]. Yin et al. produced activated carbon from coconut fibers with KOH as a chemical activator. This product exhibits a surface area of 2898 m<sup>2</sup> g�<sup>1</sup> (pore volume of 1.59 cm<sup>3</sup> g�<sup>1</sup> , i.e. 30% of mesoporosity) and specific capacitance of 266 F g�<sup>1</sup> at 0.1 A g�<sup>1</sup> in KOH 6.0 mol L�<sup>1</sup> [28]. Another biomass used to produce activated carbon is the garlic skin activated with KOH, this material presents a surface area of 2818 m<sup>2</sup> g�<sup>1</sup> , exhibiting excellent electrochemical performance and cycle stability at a current density of 0.5 A g�<sup>1</sup> (specific capacitance of 427 F g�<sup>1</sup> or 162 F cm�<sup>3</sup> ) and a retention capacitance of 94% [17].

Remarkably, the use of H3PO4 as activator leads to a lower surface area in comparison to those obtained using KOH or ZnCl2. It implies a controlled porosity in the mesopore range. The addition of H3PO4 activator also enables to obtain surfaces composed of different functional groups such as quinones and phosphide groups -C-O-P-, which subsequently decompose into CO at ̴860°C. In addition, with this activation type, large capacitance values can be obtained, all due to the nature of the phosphorus functional groups in the carbon structure [23].

Another source of biomass as coconut was also activated using NaOH. In this case, Sesuk et al. showed that the carbon material presented a surface area of 2056 m<sup>2</sup> g�<sup>1</sup> and specific capacitance of 192 F g�<sup>1</sup> at 1.0 A g�<sup>1</sup> [29].

Orange peels in copper carbonate (CuCO3) were also used to produce activated carbon. These materials present a surface area of 912 m<sup>2</sup> g�<sup>1</sup> and specific capacitance of 375 F g�<sup>1</sup> (current density of 1.0 A g�<sup>1</sup> ) [22].

Among the great variety of surface functional groups able to be incorporated on the material surface we can mention: OH�, COOH�, CO, as well as adsorbed molecules [25]. These functional groups increase their electron affinity in the aqueous medium, inducing electrochemical reactions [26, 30], which shows that their specific capacitance could be improved by addition of a pseudocapacitive component due to reversible faradaic redox involved in this type of molecules. In **Figure 2**, the optimized structures of 2,7-dimehtyl-9,10-phenanthrenequinone and its reduced form, adsorbed on a graphene surface obtained by density functional

#### **Figure 2.**

*Optimized structures of 2,7-dimehtyl-9,10-phenanthrenequinone (a) and its reduced form (b) adsorbed on a graphene surface, at the M06-2X/6-311G(d,p) level of theory. Distances in Angstroms.*

theory (DFT) calculations at the M06-2X/6-311G(d,p) level of theory, are presented.

#### **2. Reduced graphene oxide modified carbon Fibers**

In the search for a low-cost electrode, with large surface area and optimal charge retention capacity, it has been found that carbon fiber or cotton exhibits adequate surface area properties and mechanical and electrochemical stability, in comparison with other porous carbon-based electrodes [31]. Certainly, different authors have reported that the micro and macro-porosity are formed during the lignite carbonization on cotton, but the tubular structure of the cellulose fibers is not altered in the pyrolysis process [32]. In this way, carbon cotton electrodes present a large surface area related to its micro and macro-porosity [31]. Another advantage linked to the production of these electrodes is the low cost and ease synthesis, *e.g.* Sheng-Heng et al. have reported commercial cotton carbonization at 900°C under Ar atmosphere for 6 h, with area of 805 m<sup>2</sup> g<sup>1</sup> and average micropore size of 1 nm [33]. On the other hand, H. Wang et al. have obtained activated cotton carbons from cotton pieces treated with solution of KOH-H2O or KOH-urea-H2O at 700°C for 2 h under N2 atmosphere. These activated cotton carbons show 1286 m<sup>2</sup> g<sup>1</sup> of surface area and high electrochemical stability after several charge–discharge cycles as cathode in Li-S batteries [31].

In previous studies, the influence of reduced graphene oxide (r-GO) on carbon cloths and its capacity to charge store and stability have been studied. The carbonization of cotton fibers impregnated with graphene oxide at 1000°C for 2 h shows a reversible charge–discharge behavior of 160 mA h g<sup>1</sup> after 100 cycles [34]. In contrast, the design of carbon fiber material doped with nitrogen reports an outstanding stability after 200 charge–discharge cycles at 1 A h g<sup>1</sup> [34–36]. To a better understanding of modified carbon cotton cloths with r-GO on electrochemical performance, carbon cotton cloths were synthetized with r-GO 3 mg mL<sup>1</sup> , and the effect of inert atmosphere was evaluated. To achieve this, commercial cotton fibers were impregnated with graphene oxide (GO) during 0, 15, 30 and 45 min, after dried at 60°C the samples were pyrolyzed at 800°C (3°C min<sup>1</sup> ) for 30 min under

*Biomass-Based Carbon Electrodes in the Design of Supercapacitors: An Electrochemical… DOI: http://dx.doi.org/10.5772/intechopen.97649*

N2 or Ar atmosphere to obtain N/CC and N/CC/rGO5-45, or Ar/CC and Ar/CC/ rGO5-45 electrodes, respectively (**Figure 3**).

According to the EDS analysis, cotton fibers (COT) report a carbon mass percent (% m of C) of 49.1%, which increases to 63.9% after the GO impregnation stage for COT/GO45, presumably due to the presence of GO sheets on the cotton fibers surface. Similarly, after the heat treatment there is a carbon content increment of 95.6% for Ar/CC. This large increase has been associated with the CO bonds breaking during the cellulose fiber polymerization process when it is treated at temperature higher than 400°C [37], but without an apparent alteration of the fibrillary structure. The same behavior is observed for carbonized fibers covered by rGO, with values of 90.7% (N/CC/rGO45) and 92.87% (Ar/CC/rGO45) of carbon mass (% m of C), suggesting that the reduction of oxygenated groups in COT and the GO is higher under Ar atmosphere (**Table 1**). This implies that the composition, crystallinity, and porosity of carbonaceous electrodes are dependent on the atmosphere used during carbonization. Both N2-made and Ar-made electrodes have a similar fibrillary structure as seen in **Figure 4a** and **c**. However, at high magnification, it is observed that samples N/CC/rGO5-45 and Ar/CC/rGO5-45 present a rough surface covered by a porous carbon layer, which would indicate that the rGO sheets were inserted efficiently and independently of the gas used in the heat treatment (**Figure 4b** and **d**). There are marked differences between both systems where samples treated under N2 atmosphere present a more compact rough surface with a rather scaly appearance (**Figure 4b**). On the other hand, those heat treated under Ar atmosphere show layers of rGO with a laminar appearance around the fiber and regions of homogeneous roughness (**Figure 4d**).

IR spectroscopy permits to elucidate the type and degree of GO-COT, and rGOcarbon fibers (CC) interactions. The main vibrational modes corresponding to the

#### **Figure 3.**

*Schematic diagram of the synthesis of rGO-modified carbonized cotton fibers.*


#### **Table 1.**

*Carbon and oxygen mass percent obtained from EDX analysis for COT, COT/GO45, N/CC, Ar/CC and Ar/ CC/rGO45 samples [38].*

#### **Figure 4.**

*SEM image of rGO-modified carbonized made fibers made under N2 atmosphere (a, b) N/CC/rGO45, and Ar atmosphere, (c, d) Ar/CC/rGO5-45.*

#### **Figure 5.**

*Infrared and Raman spectra of (a, b) cotton fibers (COT) and GO-covered cotton fibers (COT/GO5-45) and rGO-modified carbonized cotton fibers made under N2 atm. (N/CC and N/CC/rGO5-45) or Ar atm. (Ar/CC and Ar/CC/rGO5-45). Raman laser source excitation of 532.5 nm.*

*Biomass-Based Carbon Electrodes in the Design of Supercapacitors: An Electrochemical… DOI: http://dx.doi.org/10.5772/intechopen.97649*

characteristic chemical bonds present in COT are reported before and after the impregnation (COT and COT/GO5-45) and the carbonization stage (N/CC/rGO5-45 and Ar/CC/rGO5-45), respectively (**Figure 5**). After the first stage, it is observed that the chemical groups C=O (1033.8 cm<sup>1</sup> ), CH2 (1322.2 cm<sup>1</sup> ), C=O (1639.5 cm<sup>1</sup> ), C-H (2893.2 cm<sup>1</sup> ) and O-H (cellulosic, 3325.3 cm<sup>1</sup> ) present an intensity reduction which could be correlated with GO layer. This reduction can also be associated with the interaction between the functional groups of GO and cellulose fibers. Since the cellulose OH and C=O groups register a decreasing in their intensities, it can be assumed that there exists a direct interaction between these chemical groups by hydrogen bonds [38]. According to IR spectroscopy, the bands at 979.8 and 1512.2 cm<sup>1</sup> are related to C-Cring and C=C bonds, respectively, verifying a certain degree of graphitization. This thermal conversion has been described by M. M. Tang et al. who found that cellulose in cotton fibers undergoes a breakdown of the glycosidic bonds at temperatures above 250°C, allowing the elimination of various CO bonds and the breakdown of several C-C bonds along with a substantial mass loss due to H2O, CO and CO2 removal [39]. When the temperature is greater than 400°C, the remaining fractions of C-H hydrocarbon rings start an aromatization stage with H2 loss and the formation of C=C bonds as part of a carbon polymeric structure [37]. It is observed that the conversion process to a graphitic like structure is similar for N/CC/rGO5-45 and Ar/CC/rGO5-45 (**Figure 5**).

The analysis of Raman spectra from **Figure 5b, d** and **f** show that N/CC/rGO5-45 electrodes present a slight improvement in their crystallinity with respect to the modified cotton fibers, reporting a crystallite size from 19.39 (COT/GO30) to 20.10 nm (N/CC/rGO30), that is, an improvement of 4 to 5% (**Figure 6**). This behavior is also observed in the variation of the defect density from Ar/CC to Ar/CC/rGO5-45 and from N/CC to N/CC/rGO5-45.

For instance, Ar/CC/rGO30 register 21.9 <sup>10</sup><sup>10</sup> defects cm<sup>2</sup> compared to N/CC/rGO30, whose value was 21.1 <sup>10</sup><sup>10</sup> defects cm<sup>2</sup> (**Figure 6**). According to Yo-Rhin Rhim et al. the peaks centered at 1620 cm<sup>1</sup> , between 1500 to 1550 cm<sup>1</sup> and about 1100 cm<sup>1</sup> , are associated with ordered π bonds, sp<sup>2</sup> amorphous systems,

**Figure 6.**

*3D graph of defect density (nD) as function of I(D)/I(G) ratio and crystallite size (La) from Raman spectroscopy analysis.*

and sp3 bonds, respectively. Additionally, the systems under study were treated at 800°C, the restoration of the C=C bonds in the RGO is guaranteed and remains stable inside of the carbon fiber matrix [32]. Similarly, Ar/CC and Ar/CC/rGO5-45 electrodes show a slight increase in crystallite size, for example, Ar/CC/rGO30 registered a value of 19.5 nm in contrast to that reported for its precursor COT/ GO30, i.e., 19.39 nm **(Figure 6**). Although this variation is small, the effect of the carbonization stage is better appreciated when defect density is compared, e.g., Ar/ CC/rGO30 shows 21.8 <sup>10</sup><sup>10</sup> defects cm<sup>2</sup> while COT/GO30 was 21.9 1010 defects cm<sup>2</sup> . This result means that the GO sheets supported on the cotton fibers present an excess of 0.1 <sup>10</sup><sup>10</sup> defects cm<sup>2</sup> compared to Ar/CC/rGO30 sample. It can thus be suggested that the nature of the inert atmosphere influences the degree of graphitization of the obtained products. Under N2 atmosphere, a higher crystallinity is observed in N/CC/rGO5 with a value equal to 20.3 nm and a defect density of 20.9 <sup>10</sup><sup>10</sup> defects cm<sup>2</sup> . In the case of cotton fibers modified with GO treated under Ar atmosphere, the optimal registered support is Ar/CC/rGO15 with a crystallite size of 19.6 nm and a defect density of 21.6 <sup>10</sup><sup>10</sup> defects cm<sup>2</sup> .

According to IR and Raman analysis, it is confirmed that GO sheets are intimately impregnated on cotton fibers through O-H or C=O interactions, and this interaction intensifies after the carbonization stage [38]. This effect is corroborated as an increase in crystallinity and a decrease in the density of defects (**Figure 6**). Therefore, through Raman spectroscopy it is possible to elucidate those carbonaceous materials that present a higher degree of crystallinity, lower defect density and higher density of sp2 carbons which providing a high electrical conductivity. The evidence from these results suggests that samples such as N/CC/rGO5, N/CC/ rGO30, Ar/CC/rGO5 and Ar/CC/rGO30 are shown as promising matrices in the design of supercapacitors.

On the other hand, N2 adsorption–desorption experiments were used to investigate the surface characteristics of the synthesized samples. It was possible to determine the specific surface area (SBET), the degree and porosity type of the designed materials. In the case of N/CC presents a SBET of 453.3 m<sup>2</sup> g<sup>1</sup> , shaped of a microporous area (Smicro) of 265.9 m<sup>2</sup> g<sup>1</sup> and with a size pore of 1.99 nm (**Table 2**). Furthermore, N/CC/rGO15 and N/CC/rGO30 exhibit SBET values of 1221.3 and 1804.8 m<sup>2</sup> g<sup>1</sup> , respectively. These values suggest the presence of a highly porous rGO layer on carbonized cotton fibers prepared under N2 atmosphere. Specifically, a high microporosity of 882.4 and 1350.2 m<sup>2</sup> g<sup>1</sup> is reported for the N/CC/rGO15 and N/CC/rGO30, respectively, as a consequence of a large volume of micropores with diameters close to 1.88 nm (N/CC/rGO15) and 1.80 nm (N/CC/rGO30). Similarly, there was an increase in the SBET from 1073.6 to 1457.5 m<sup>2</sup> g<sup>1</sup> , but with a substantial increase in mesoporosity from 298.6 to 729.8 m<sup>2</sup> g<sup>1</sup> for the Ar/CC and Ar/CC/


#### **Table 2.**

*Surface properties registered by N2 adsorption–desorption experiment [38].*

*Biomass-Based Carbon Electrodes in the Design of Supercapacitors: An Electrochemical… DOI: http://dx.doi.org/10.5772/intechopen.97649*

**Figure 7.**

*N2 adsorption–desorption isotherms and pore size distribution of carbonized cotton fibers made under (a, b) N2 atmosphere. (N/CC and N/CC/rGO5-45) and (c, d) Ar atmosphere. (Ar/CC and Ar/CC/rGO5-45).*

rGO15, respectively **(Figure 7c**). Additionally, it was observed that the Ar/CC/ rGO15 presents a balance between micro and mesoporosity with a ratio of 1: 1, in contrast to Ar/CC (2.6: 1) and Ar/CC/rGO30 (1.9: 1). It can therefore be asserted that the electrochemical properties could be modified in the same way and correlated with the aforementioned texture properties [10].

Regarding to cyclic voltammetry test, a layer capacitive profile for N/CC (**Figure 8a**), Ar/CC, Ar/CC/rGO15 and Ar/CC/rGO30 (**Figure 8b**) is observed, while an increment of resistivity for N/CC/rGO15 and N/CC/rGO30 is registered

#### **Figure 8.**

*Cyclic voltammetry of (a) N/CC, N/CC/rGO15 and (b) Ar/CC, Ar/CC/rGO15 and Ar/CC/rGO30 at 1.0 mV s<sup>1</sup> in H2SO4 1.0 Mol L<sup>1</sup> . Charge–discharge test of (c) N/CC, (d) Ar/CC, (e) N/CC/rGO15 and (f) Ar/CC/rGO15 at 1.5, 3.0, 6.0 and 12.0 mA for 120 s.*

(**Figure 8a**) [10]. This fact represents a reduction of N2-made electrodes specific capacitance (Cs) from 70.3 (N/CC) to 45.3 F g�<sup>1</sup> (N/CC/rGO15), revealing a growing capacitive current for Ar-made electrodes at same potential range from 69.6 (Ar/CC) to 197.8 F g�<sup>1</sup> (Ar/CC/rGO15), as maximum. Both tendencies can be associated to the micro/mesoporosity ratio (*Smicro=Smeso*) showed in **Table 2**, owing to the high pore free energy that restricts the ionic charge transfer in the electrodeelectrolyte interface [34, 40]. Thus, a high microporosity implies a limited ionic polarization at non-faradaic conditions, and a low capacitive charge retention [41]. In addition, capacitive current can be increased if the mesoporous surface area is extended, as it has been seen for Ar-made electrodes.

According to galvanostatic charge–discharge test (GCD) [42, 43], specific capacitance (*CGCD*) of N/CC tends to decrease while the impregnation time increases (**Figure 8c**). This fact can be associated to the microporous surface area (*Smicro*) increase, as shown in **Figure 8c** and **e**. This can also be attributed to the presence of series-resistance in the pores (IRS) [34, 40]. Particularly, *CGCD* decreases from 178 to 162 F g�<sup>1</sup> at 0.4 A g�<sup>1</sup> of applied current density for N/CC and N/CC/rGO45, respectively (**Table 3**). On the other hand, if the inert atmosphere is replaced by Ar flux at the same thermal treatment conditions, Ar/CC shows a capacitive current increment with the impregnation time (**Figure 8d** and **f**). For instance, Ar/CC shows a *CGCD* of 129 F g�<sup>1</sup> , while its rGO-modified electrode, Ar/CC/rGO15, reports a value of 219 F g�<sup>1</sup> at 0.4 A g�<sup>1</sup> (**Table 3**).

A detailed analysis of the electrochemical behavior by electrochemical impedance spectroscopy (EIS) experiments and non-linear complex fitting (NLCF) of their equivalent circuits has been conducted. Nyquist diagrams show an electrolyte resistance (*RS*) of 2 Ω approximately, as well as, non-ideal impedance loop for both N2-made and Ar-made electrodes suggesting a non-ideal charge storage process at the electrochemical interface [44, 45].

Regarding to N2-made electrodes, charge transport resistance (*R*1) increases with the GO impregnation time at high frequencies range (10<sup>4</sup> –10<sup>2</sup> Hz) (**Figure 9a**). NLCF shows that *R*1value varies from 5.6 (N/CC) to 100.3 Ω (N/CC/ rGO30), as maximum. Moreover, at medium frequencies range (102 – 10�<sup>1</sup> Hz) N/CC electrode shows an *IRS* of 6.3 *Ω*, whereas N/CC/rGO15 reports values of 33.6 *Ω* and N/CC/rGO30 present an *IRS* conformed by two circuit elements, *R*<sup>2</sup> and *R*<sup>3</sup> whose values are 125.8 *Ω* and 149.3 *Ω*, respectively. These results suggest that ionic transport resistance in the inner porous surface is increased from N/CC/rGO15 to N/CC/rGO30 as their microporosity becomes higher [46–48].

For the Nyquist diagram (**Figure 9**) the equivalent circuit was calculated, resulting in ideal capacitive element ð Þ *<sup>C</sup>*<sup>1</sup> of 4.8 x 10�<sup>5</sup> for N/CC/rGO30. This result can be associated to the presence of the rGO layer on the fiber surface [49]. According to the transmission line model, N/CC/rGO30 internal capacitances are represented by constant phase elements (*Q*2, *Q*3), where their behavior is related to


#### **Table 3.**

*Double layer electrochemical capacitance by galvanostatic charge–discharge test (CGCD) for N2- and Ar-made electrodes [38].*

*Biomass-Based Carbon Electrodes in the Design of Supercapacitors: An Electrochemical… DOI: http://dx.doi.org/10.5772/intechopen.97649*

**Figure 9.**

*Nyquist diagram of N2-made electrodes (a) N/CC, N/CC/rGO15 and N/CC/rGO30 and Ar-made electrodes (b) Ar/CC, Ar/CC/rGO15 and Ar/CC/rGO30. Experimental (empty dots) and theoretical spectra (solid lines).*

a non-ideal capacitor [44, 46]. Interestingly, the internal capacitance shows a minimum value of 0.2 *Ω*�<sup>1</sup> *s <sup>α</sup>*<sup>2</sup> (*α*2, 0,90) for N/CC/rGO30 (**Figure 10a**) [50]. Furthermore, N/CC/rGO5 and N/CC/rGO45 show a similar correlation with the impregnation time.

Besides, Ar-made samples report lower charge transport resistance (*R*1) than N2-made electrodes. For instance, Ar/CC shows a *R*<sup>1</sup> of 5.8 *Ω*, while Ar/CC/rGO15 reports a value of 2.1 and Ar/CC/rGO30 registers a *R*<sup>1</sup> of 2.8 *Ω*. As well, *IRS* is represented by a unique circuit element (*R*2) of 12.8 and 7.3 *Ω* for Ar/CC/rGO15 and Ar/CC/rGO30, respectively. Remarkably, Ar-made samples report a laminar mesoporosity, suggesting that ionic diffusion is controlled by the pore characteristics. Hence, a finite diffusion element (*M*) is used to describe the capacitive behavior at low frequencies (**Figure 10b**) [46, 47, 50]. In this sense, Ar/CC/rGO15 presents a constant phase element (*Q*3<sup>Þ</sup> of 0.6 *<sup>Ω</sup>*�<sup>1</sup> *<sup>s</sup> <sup>α</sup>*<sup>3</sup> (*α*3, 0.99), and a Warburg impedance (*W*) of 0.3 *Ω*�<sup>1</sup> *s* <sup>0</sup>*:*5. On the other hand, Ar/CC/rGO30 presents a non-

#### **Figure 10.**

*Equivalent circuit of (a) N/CC/rGO30, (b)Ar/CC/rGO30. The inserted values are calculated from non-linear complex fitting of the EIS measurements.*

ideal capacitance of *Q*<sup>3</sup> of 0.7 *Ω*�<sup>1</sup> *s <sup>α</sup>*<sup>3</sup> (*α*3, 0.99) together to diffusion impedance *W* of 0.3 *Ω*�<sup>1</sup> *s* <sup>0</sup>*:*<sup>5</sup> (**Figure 10b**). In contrast, Ar/CC only shows an ideal capacitive behavior of 3.0 x 10�<sup>5</sup> F (*Cdl*) and internal one of 0.2 F.

Accordingly, the total capacity (*CEIS*) from the internal capacitive element (*Q<sup>α</sup> EIS*) is reported where the non-ideal constant (*α*) tends to one. For the estimation of the electrochemically accessible surface (*SEIS*), a double layer charge density (*Q<sup>o</sup> dl*) of glassy carbon electrode of 3.0 x 10�<sup>5</sup> F cm�<sup>2</sup> is considered [51, 52],

$$\mathbf{S\_{EIS}}\left(m^2 \mathbf{g}^{-1}\right) = \mathbf{Q\_{EIS}^{a \approx 1.0}} / \left(m \mathbf{x} \mathbf{Q\_{dl}^o}\right) \tag{6}$$

Additionally, the electrochemically accessible surface ratio (*RESA*) registers the fraction of interface surfaces available in the total physical surface area (*SBET*) [52].

$$R\_{ESA} = \mathbb{S}\_{EIS} / \mathbb{S}\_{BET} \tag{7}$$

The difference between *CEIS* and *CGCD* values show the total charge related to the electrochemical double layer, whereas the GCD test also registers the faradaic charge caused by the surface carbon and oxygen groups [52, 53]. As we can observe in **Table 4**, N2-made samples present a decrease of the *RESA* (from 0.6 to 0.2) which can be related to the increment of the free energy adsorption promoted by their microporosity. The opposite occurs in Ar-made electrodes where *RESA* increases (from 0.2 to 0.4) and it can be related to their laminar mesoporous surface which results in a controlled ionic diffusion. Based on the *RESA* results, Ar/CC/rGO15 and Ar/CC/rGO30 electrodes emerge as promising candidates for the design of supercapacitors.

The aforementioned results enable us to conclude that the inert atmosphere has a strong influence on the surface and electrochemical characteristics of the synthetized carbon-based electrodes. Under N2 atmosphere, N/CC and N/CC/ rGO5-45 show a remarkable microporous surface area. Unfortunately, this high microporosity affects the ionic diffusion, capacitive behavior and resistive character. Otherwise, under Ar atmosphere, an increase of the mesoporous surface is reported, based on a laminar pore distribution, associated with controlled ionic diffusion in the electrochemical cell, resulting in an increase of the capacitance.


#### **Table 4.**

*Comparative chart between double layer electrochemical performance and superficial characteristics for N2 and Ar-made carbon-based electrodes [38].*

*Biomass-Based Carbon Electrodes in the Design of Supercapacitors: An Electrochemical… DOI: http://dx.doi.org/10.5772/intechopen.97649*

Remarkably, both Ar/CC/rGO15 and Ar/CC/rGO30 exhibit a promising capacitive behavior, as well as an optimal electrochemical accessible surface.

In this sense, the design of carbon-based electrodes from biomass-derived materials represents an outstanding way to obtain several energy-store electrochemical systems [54–56]. In addition, a remarkable capacity retention depending on pore size distribution looks like a constant effect on the constitution of double layer interface (DLI).

For instance, L. Jiang et al., reported a high performance of cellulose-derived microporous electrodes of 115 F g<sup>1</sup> and > 87% of capacity retention [54]. As well, Y. Zou et al., described rGO-intercalated carbon cloth fibers electrodes with a meso/micro-porous distribution and 64.5 mF cm<sup>2</sup> of specific capacitance [55]. Sheng-Heng C. et al. show that macro/micro-porosity to carbonized cotton fibers produce carbons with notable surface area [56]. On the other hand, Hui Shao et al., have paid special attention to nanoscale pores on carbon materials obtained by templates and double layer capacitance behavior at inside of this nanoscale pores [57]. Therefore, this fact is still discussed, owing to non-clear description is achieved by a cylindrical pore model in overall cases. Other parameters as the kind of inert atmosphere are considered in this work. Herein, a brief explanation of porosity-electrochemical performance is described, and inert atmosphere influence has been exposed as a significant parameter, as well as gas flux and temperature, certainly [38, 39].

#### **Acknowledgements**

The authors wish to thank the Vice-Rectorate of Research of National University of Engineering (UNI), Contract P-CC-2021-000546, and the Peruvian government agencies CONCYTEC and FONDECYT /World Bank (ref. 026-2019 FONDECYT-BM-INC.INV).

#### **Conflict of interest**

The authors declare no 'conflict of interest'.

*Supercapacitors for the Next Generation*

#### **Author details**

Antony Bazan-Aguilar<sup>1</sup> , Elvis O. López2 , Miguel Ponce-Vargas<sup>3</sup> and Angélica M. Baena-Moncada<sup>1</sup> \*

1 Research Laboratory in Applied Electrochemical, National University of Engineering (UNI), Lima, Peru

2 Department of Experimental Low Energy Physics, Brazilian Center for Research in Physics (CBPF), Rio de Janeiro, Brazil

3 Institut de Chimie Moléculaire de Reims UMR CNRS 7312, Université de Reims Champagne-Ardenne, Reims, France

\*Address all correspondence to: abaenam@uni.edu.pe

© 2021 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

*Biomass-Based Carbon Electrodes in the Design of Supercapacitors: An Electrochemical… DOI: http://dx.doi.org/10.5772/intechopen.97649*

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#### **Chapter 3**

## Biomass Based Materials in Electrochemical Supercapacitor Applications

*Sema Aslan and Derya Bal Altuntaş*

#### **Abstract**

Biomass is the general term for organic substances derived from living organisms (plants and animals). Since, biomass is a renewable, sustainable, innovative, low cost and carbon-neutral energy source, the applications of nano-micro particles produced from biomass in electrochemical applications have emerged. A large number of carbon-based materials, such as featured activated carbon, carbon nanotube, C-dots, biochar, hybrid carbon-metal/metal oxide … etc. can be produced from divergent types of biomass. With the growing energy need in the world, supercapacitors have also developed considerably besides the energy generation and storage methods. The supercapacitor is an energy storage system that can work reversibly to provide high energy in a short time. In these systems, electrode structure and surface properties are crucial for energy capacity enhancement. In this sense, electrode modifications with the above-mentioned biomass-based nano-micro structures are widely used in supercapacitor applications.

**Keywords:** Biomass, carbon, energy, electrochemistry, supercapacitor

#### **1. Introduction**

Biomass is defined as all biomass of non-fossil organic matter of biological origin, which can be renewed in less than 100 years, includes land and water-grown plants, animal wastes, food industry, and forestry by-products, and urban wastes [1]. Energy obtained from biomass sources such as vegetable resources, agricultural and animal wastes, organic origin city, and industrial wastes is defined as biomass energy. Since the basis of biomass energy is based on the photosynthesis of plants, biomass energy can also be expressed as the energy of organic matter where solar energy is stored as chemical energy [2].

Vegetable or animal biomass energy sources that can be found in the sea and/or land can be queued as; wood (energy forests, wood residues), oilseed crops (sunflower, rapeseed, soy, safflower, cotton, etc. …), carbo-hydrate plants (potato, wheat, corn, beet, etc. …), fiber crops (flax, kenaf, hemp, sorghum, etc. …), vegetable residues (branches, stalks, straw, roots, bark, etc. …), animal wastes, urban and cleans [1–3]. Biomass resources are of high water and oxygen content, low density, low calorific value; These features negatively affect the quality of loss [4]. The negative properties of biomass can be eliminated by physical processes (size reduction-crushing and grinding, drying, filtration, aggregation) and transformation

processes (biochemical and thermochemical processes) [5]. Biomass energy stands out with its various advantages such as the ability to be grown almost everywhere, good knowledge of production and conversion technologies, suitability for energy production every time, adequacy of low light intensities, being storable, adequacy of temperatures between 5 and 35°C, being in socioeconomic developments, not creating environmental pollution (Very low NOx and SO2 emissions), less greenhouse effect formation compared to other energy sources, cream of CO2 balance in the atmosphere, not causing acid rain [1–6].

#### **2. Nanomaterials**

Studies on nanoscale materials have shown very great improvement and received much attention for decades. Structures are defined as nanoscale materials; Nanocrystals are divided into different classes such as nanoparticles, nanotubes, nanowires, nanorods, or nano-thin films. The main reason for the focus on this subject is that the substances exhibit unusual properties and functionality in a certain size range, unlike their volumetric structures [7, 8]. On the other hand, nanoparticles, which are defined as powders with a size of 100 nm or less, form the basis of nanotechnology due to nanosized materials. These particles show properties that are generally considered different and superior to other commercial materials. The reasons known today for the attractiveness of the frequently mentioned nanoparticle properties are; Quantum size effects stand out as the size dependence of the electronic structure, unique characters of surface atoms and high surface/volume ratio [9].

Nanoparticle synthesis has paved the way for the preparation of many technological and pharmacological products such as high-activity catalysts, special technological materials for optical applications, superconductors, anti-wear additives, surfactants, drug carriers and special diagnostic tools, due to the extraordinary properties these structures exhibit. In addition, the control of materials at the nanoscale level allows the realization of miniaturized devices with specific functions such as nanocarriers, sensors, nanomachines and high density data storage cells [8–10]. The indispensable first step for new developments in nanotechnology, which includes the design, manufacture and functional use of nanostructured materials and devices, is the production of nanoparticles. Nanoparticles, which form the starting point of nanotechnological materials, can be produced in a wide chemical range and morphology. Today, nanoparticles with different morphologies such as core-shell, doped, sandwich, hollow, spherical, rod-like and polyhedral can be prepared from metal, metal alloy, ceramic and polymer-based or mixtures with the desired properties [10–12].

#### **2.1 Biomass based carbon nanomaterials**

Biomass is a very low cost carbon source and is used in the production of high value carbon nanomaterials [1–3]. While biochar, activated carbon and mesoporous graphite come first among these materials, when advanced processes are applied, graphene, graphene oxide, carbon nanotubes, carbon-based nanostructures and even hybrid nanostructures containing metalloxide can be successfully produced (**Figure 1**) [13–18].

In particular, biochar, activated carbon and porous carbon production from biomass and their various applications were very popular [16–21]. In one of these studies biochar is synthesized from hair and then activated charcoal without any chemical treatment [19]. The same group reported the synthesis and characterization *Biomass Based Materials in Electrochemical Supercapacitor Applications DOI: http://dx.doi.org/10.5772/intechopen.98353*

**Figure 1.** *General flowchart of the green synthesis of high value added carbon materials from the biomass.*

of the activated carbon again from waste human hair mass successfully by using chemical activation [20]. Although biochar has a developed porous structure, it shows the limited specific surface area, and activated charcoal has an uncontrolled pore size distribution and irregular three-dimensional structure, which has greatly limited their use in specific applications. For this reason, new generation composite carbon structures originating from biomass were developed, and materials with superior thermal and electrical conductivity and good chemical and environmental stability were developed [22–24]. Later, graphene, graphene-like nano-layers were developed from structures such as activated charcoal obtained from biomass, whose pore structure progressed in a stable pattern with good electrical conductivity, and whose pore structure did not differ [16–22]. Also, Wang et al. [25] reported that the microwave plasma beam method can be utilized to create graphene CNT hybrids.

#### **3. Supercapacitors**

The need for energy is increasing day by day and the resources used for energy production are rapidly being depleted. Although the types of resources used in energy production vary, the dominant resources are still petroleum-based fossil fuels [26]. The greenhouse gases released while obtaining energy from these fuels threaten the ecosystem seriously. In this sense, energy storage has gained importance as well as energy production. The methods used for energy storage can be listed as ultracapacitors/supercapacitors, superconducting magnetic energy storage, fuel cells, and batteries [27]. Among these, supercapacitors have an important place. Supercapacitors are also known as secondary batteries used as energy storage and conversion systems. It has attracted great attention in recent years due to its high power density and long cycle life compared to rechargeable batteries [28]. Supercapacitors can be classified as electrical double layer capacitors, pseudocapacitors and hybrid capacitors. The most important factor in improving the performance of supercapacitors is the electrode used [27–29]. Many modifications have been developed to load on the electrode surface and to keep this charge in the double layer for the desired time, that is, to provide charging and discharging when needed. Conductive polymers [30], nanofibers [31], graphene and graphene oxide [32], carbon-based [19] or metal–metal oxide derivative hybrid [33] or nanostructures of different sizes and many other types of modifications.

#### **3.1 Biomass based materials in supercapacitors**

Carbon based materials occupy a respectable area on the electrode development in electrochemical energy devices. In general, the source and production methods of carbon-based materials used in batteries, capacitors, supercapacitors and fuel cells have gained importance [34]. The ability to obtain carbon-derived composite or single materials that exhibit superior properties from biomass has made an important contribution to this field. The materials produced to provide high capacitance, fast response and high cycle number, especially in supercapacitor applications [34, 35]. Especially the large surface area due to the porous structure of the carbon-based materials obtained and the ability to be made with an cost-effective and unlimited precursor provides a great advantage [34–42].

Senthil et al. [36] previously examined changes in supercapacitor performance by using the tubular porous carbon material (HT-PC) they produced using waste feather grass flower (FFGF) in electrode modification. They reported a very high specific capacitance value around 300 F g−1 with HT-PC containing electrode. Additionally, they obtained % 96 capacitance conservation after 50000 cycles whereas the electrolyte solution is changed from KOH to 1 M Et4NBF4/AN electrolyte they observed % 30 capacitance loss over 10000 cycles. This is noted as a very appreciatable recovery for capacitance conservation. In another flower based study is reported by Zheng et al. [37]. They used waste-kapok flower as a precursor to produce hierarchically porous carbon as supercapacitor electrode. Here the authors took the advantages of the oxygen rich structure of the kapok flower to obtain micro and meso porous carbon structure. The KOH electrolyte using supercapacitor achieved around 290 F g−1 supercapacitance value and showed excellent cyclic stability.

Activated carbons are one of the most popular carbon materials for commercial supercapacitors. Jain et al. [38] reported t a cavitation process of the activated carbon from the mixture of native European deciduous trees, Birch, Fagaceae, and *Carpinus betulus* (commonly known as European hornbeam). They reported a desirable carbon with enhanced porosity and high specific surface area of about 614 m2 g− 1. Here they examined the supercapacitance of the synthesized activated carbon as an additive to electrode structure in acidic 1.0 M H2SO4 electrolyte. Finally, they showed that the reported method is suitable to achieve a versatile electrode material for supercapacitors.

The hydrothermal method is also a green synthesis method for biomass based productions. Nguyen et al. [39] utilized a carbonization method to synthesize a high-surface-area carbon (HSAC) material from the peanut shells. The HSAC growth on the Ni foam and obtained material achieved nearly two times higher specific surface area than the activated carbon which is produced by Jain et al. Besides they processed the supercapacitor application in KOH and 1 M Li2SO4 electrolyte and obtained a highly desirable capacitance value around 250 F g−1. This is a very unique example of a completely green synthesis of carbon based materials in terms of the source and the processed method. Another impactive biomass based supercapacitance materials are carbon aerogels. They possess highly multifunctional features including compressibility and elasticity. Differently, Long et al. [40] used the calcinated mixture of glucose & dicyandiamide nanosheets (C-GD) and cellulose nanofibers (CNFs) to synthesize nitrogen doped carbon aerogels (C-NGD). C-GD and CNFs lead to a super stable wave-layered structure with an ultimate compression strain (95%) and dedicated as a potential multifunctional material toward flexible electronics, and energy conversion/storage devices.

The porosity of the developed carbon material is very crucial for catalytic applications. To achieve a better regularity in the pore size and distribution divergent

#### *Biomass Based Materials in Electrochemical Supercapacitor Applications DOI: http://dx.doi.org/10.5772/intechopen.98353*

methods are developed. This is very important to obtain consistent activities from the contributed material. In one of these studies, Wu et al. [41] reported that by using melamine foam it is possible to obtain hierarchical porous carbon. They used the waste liquid of the vitamin-C production as the precursor and obtained highly porous carbon by using this template. They used KOH activation on the precursor, and the porous material showed excellent supercapacitance value as 217 F g−1 in 1-ethyl-3-methylimidazolium tetrafluorobo- rate (EMIMBF 4) electrolyte. The cycling stability of the material amendable and the energy and power densities are evaluated as impactive by the authors (**Table 1**). A considerable part of this study is the utilization of the developed material in all-solid state state symmetric supercapacitors and obtained attainable capacitance value as 180 F g−1 capacitance in gel polymer electrolyte. Because, the multiple applications of the same material enhances their potential and commercial value. Also Fang et al. [42] developed a high-performance flexible supercapacitor which is produced from carbon nanorod and carbon fiber. They used waste straw for the production of carbon nanorods supported hydrothermal carbons and carbon fibers (CNR/HTC/CFs). They reached to 270 F g −1 in solid state supercapacitor.

It is possible to apply the produced featured biomass derived carbon materials in both HER and supercapacitors to evaluate their efficiency in energy devices. Cao et al. [52] used the bean sprout to produce nitrogen doped carbon material. Both the carbon and the nitrogen source was the biomass itself. In such a process the control of the pore size and distribution can be controlled by the heat treatment. Here the self-nitrogen doped porous structure evaluated as a good electrolyte ion transferring system for the hydrogen evolution reaction (HER) and supercapacitor applications. They reported very satisfactory HER and specific capacitances and showed that bean sprout have great energy potential for the industrial scale-up with low-cost.

A large amount of the biomass based production methods are covering lignocellulosic biomass residues. Some of the pioneering studies are reported by Selvaraj et al. and Tan et al. Selvaraj et al. [51] produced the activated carbon nanosheets from *Prosopis juliflora* wood carbon waste blocks as carbon precursor. They achieved an ultra-high specific surface area with micro/meso and macro pores and gravimetric capacitances from 400 to 430 F g−1 for the different supercapacitance measurement conditions. Tan et al. [8] reported excellent specific surface area and specific capacitance values (**Table 1**) by tuning the initiator biomass material and activation agent. They processed divergent precursors such as cellulose, hemicellulose, and lignin with changing percentages of extractives. It can be clearly seen that the specific surface area enhancement directly brings the increase in specific capacitance value. Yakaboylu et al. [53] reported that the tuning of the pretreatment parameters is very important to control the final pore composition in lignocellulose based activated carbon production. They used the Miscanthus grass biomass as the precursor for the sheet-like activated carbon synthesis and obtained around 190 F g−1 capacitance value. The pore size and distribution are controlled by the KOH pretreatment and interconnected micropores are obtained. Thus, the importance of the process control comes out which affects the pore size and volume, cellulose and oxygen amount in the structure, and morphological features which are crucial for the electrochemical adsorption capacity and catalytic performances of produced carbon material.

Sometimes the produced materials can be functionalized by additional groups or heat treatment is applied to enhance the electrical performance. The addition of heteroatoms provides interconnected networks between pores. Chaparro-Garnica et al. [54] synthesized highly porous (SBET >1200 m<sup>2</sup> g−1) activated carbon from hemp residue by H3PO4-assisted hydrothermal carbonization (HTC). Then they doped the obtained activated carbon with nitrogen groups and stabilized the



#### *Biomass Based Materials in Electrochemical Supercapacitor Applications DOI: http://dx.doi.org/10.5772/intechopen.98353*

**Table 1.**
