Abstract
Supercapacitors became more and more important recently in the area of energy storage and conversion. Their large power deliveries abilities, high stability and environmental friendliness characteristics draw tremendous attention in high-power applications such as public transit networks. Carbonaceous materials with unique surface and electrochemical properties were widely used in supercapacitors as electrode materials. This review focuses on the developments in supercapacitor electrodes made from carbonaceous materials recently, their working principle and evaluation parameters were summarized briefly. The preparation methods and electrochemical properties of different carbonaceous materials were compared and classified. It was found that the surface situation (e.g., porous structure, hydrophilic) of carbonaceous materials strongly affect the electrochemical performances of supercapacitor. So far, active carbons would be the most applicable carbonaceous electrode materials owing to their good chemical stability and conductivity, extensive accessibility inexpensiveness. But their energy densities still fall behind practical demands. Both theoretical calculations and experimental studies show that surface modification and doping of carbonaceous materials can not only optimize their pore size, structure, conductivity and surface properties, but also can introduce extra pseudocapacitance into these materials. Considering global environmental pollution and energy shortage problems nowadays, we sincerely suggested that future work should focus on domestic, medical and industrial wastes residues derived carbonaceous materials and scaled production process such as reactors and exhaust gas treatment.
1 Introduction
Over the past two decade, the comsumption and cost of gradual exhausted fossil fuels were significantly increased due to industrial developments and international competitions (Sujatha, 2021). Moreover, abuse of fossil fuels have being caused environmental pollution and global warming (Welsby et al., 2021). In order to cope these crises, wind energy, solar energy and other unstable but sustainable energy sources are urgently needed (Zhang et al., 2017; ; Shao et al., 2020). Therefore, efficient installation for energy storage, including and supercapacitors (or electrochemical capacitors) and batteries, have attracted tremendous attentions. Supercapacitors have unique advantages especially in terms of wide operating temperature range, no memory effect, good cycling stability and high watt density (; ; Song et al., 2022a). The electrochemical performance comparison about supercapacitors, conventional capacitors and batteries were listed in Supplementary Table S1 (Salunkhe et al., 2016). Overall performance of supercapacitors currently lies between traditional dielectric capacitors and batteries. Generally the energy density of supercapacitors is relatively lower than that of many batteries, but the unique electricity storage process enables supercapacitors to store or release substantial amount of electricity in a very short time, which let supercapacitors become a most competitive candidate for the technologies that need are fast to transport and require a quick surge of electrical energy in a very short moment such as wind turbines, grid stabilization system, uninterruptable power supply, forklifts, military weapons, load cranes, hybrid electric vehicles, regenerative braking systems for electric vehicles and rail transit (Taberna et al., 2003; Meng et al., 2004; ; Wei et al., 2010; ; Lv et al., 2020; Hasan Md et al., 2022).
So far, the working principle of common supercapacitors and electrode materials have been fully studied. Electrical energy can be stored in the form of capacitance by supercapacitors via storing positive and negative charges on their spaced opposing electrodes. Supercapacitors falls into two categories based on different capacitance storage principles: “Electric double layer capacitors (EDLC)” and “Faraday quasi capacitors” (or named pseudocapacitors) (Luryi, 1988; Pekala, 1989; ; ; ; Stoller et al., 2011; Paek et al., 2013; ; Zhu et al., 2016; ; ; Xue et al., 2019; ; Miao et al., 2021a; Song et al., 2021a; Wang et al., 2021a; Miao et al., 2021b; Song et al., 2021b; ; Long et al., 2021; Mansuer et al., 2021; Sakita et al., 2021; Xin et al., 2021; Zhang et al., 2021; Yang et al., 2022a; ; Mansuera et al., 2022; Qin et al., 2022; Yan et al., 2022; Zheng et al., 2022; Maldonado-Hódar et al., 2000; ; ; ; Qin et al., 2009; ; Lv et al., 2012; Morteza et al., 2015; Mousavi-Khoshdel and Targholi, 2015; Mousavi-Khoshdel et al., 2016; Ping et al., 2016; Wang and Pumera, 2016; Liu et al., 2017; Song et al., 2018; Silva et al., 2020; ; ; ; ; ; ; ; Song et al., 2021c; ; Nizam et al., 2021; Olabi et al., 2021; Ramirez et al., 2021; Tong et al., 2021; Vermisoglou et al., 2021; Zhai et al., 2021; Zhou et al., 2021; Yang et al., 2022b; Mei, 2022; Rashidi et al., 2022; Teimuri-Mofrad et al., 2022; ; Paul1 and Roy, 2021; ; Zhang et al., 2019; Zhai et al., 2011; Rashidi and Yusup, 2020; Yang and Zhou, 2017; ; Umezawa et al., 2021; Mandal et al., 2021; Wulandari et al., 2021; Wu et al., 2021; Taer et al., 2021; ; Yuan et al., 2021; ; Wang et al., 2015; ; ; ; ; ; ; ; Wang et al., 2009; ; ; Sun et al., 2013; ; Long et al., 2015; ; Xiao et al., 2016; ; Tian et al., 2017; Wang et al., 2017; ; Sahoo et al., 2018; ; Tao et al., 2019; Wang et al., 2019; ; ; Wang et al., 2021b; Pang et al., 2021; Singh et al., 2021; Tatrari et al., 2021; Zhao et al., 2021; ; ; Song et al., 2022b; ; Zhai et al., 2022). As shown in Figure 1, to evaluate the performance of supercapacitors, several Electrochemical analysis methods such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge (GCD) test and were widely used. It has been found that important parameters of supercapacitors (e.g., operating potential window, equivalent series resistance and capacitance), are strongly depends on their electrode materials (; ). As shown in Figure 1A, capacitance (C) of supercapacitors could be obtained from CV curves using Eq. 1, where ΔV is the total potential bias of the voltage window, dt is the sampled span of time, i is a sampling current. If CV curves are close to ideal rectangles, C could be calculated using Eq. 2, where ν is the potential scan rate. Gravimetric capacitance (Cm) is an important parameter for supercapacitors, when CV curves of a supercapacitor show the characteristics of a non-ideal rectangle (e.g., have pseudocapacitive bulging peaks), Cm of the electrode materials could be calculated from enclosed area between the current and the voltage in the CV curve using Eq. 3, where m is electroactive materials’ mass in electrodes, I(V) denotes the density of response current, Vc and Va are CV curve’s integration limits (Wei et al., 2010). As shown in Figure 1B, the GCD curve can calculate the Cm of the electrode material (4), where Δt is the time of discharge, m is the active materials’ mass, ΔV is the change of voltage which is excluded voltage drop (IR drop) in the process of discharge, I is the current of discharge. After assembling into a symmetrical supercapacitor, the capacitance of single electrode (Cs) can be calculated through Eq. 5, where m represents the gross mass of active materials on two working electrodes, but I, t, and V reflect same meaning as Eq. 4. Volumetric capacitance (CV) and areal-specific capacitance (CA), which can be obtained according to the volume or the area of the single electrode through Supplementary Eqs S1, S2, are also important. Since the thickness of electrode materials are difficult to be measured accurately till now, compare to Cm much fewer studies reported CV or CA (; Zhao et al., 2021). EIS provides focused analysis of the resistive behavior. Solution resistance, charge transfer impedance, could be calculated from Nyquist plots’ altofrequency part (Figure 1C), while low frequency part of the curve shows the ion diffusion impedance. In addition, the Bode phase diagrams (Figure 1D) show phases angle as a function of frequency. The capacitance’s real and imaginary parts (C′(ω) and C″(ω)) can be calculated from the impedance data based on Eq. 6, where complex impedance is Z(ω), its real and imaginary parts are Z′(ω) and Z″(ω), and the angular frequency is ω (Taberna et al., 2003). There is a Eq. 7 can also be used to calculate Cm, where m is active materials’ mass in each electrode, f is the operating frequency, and Z″ and Z′ are the imaginary and real parts of total resistance (). Besides, supercapacitors’ energy density (E), power density (P) and coulombic efficiency (η) can be estimated by Eqs 8–10, where ∆V, Δtd, and Δtc denote the voltage window, discharge time and charge time (Mansuera et al., 2022).
FIGURE 1
Electrode material is a crucial component in supercapacitors. With fascinating characteristics of environmental benignity and abundance, carbonaceous materials equipped with extensive applicability and outstanding physicochemical stability have been one kind of the most popular materials that applied in supercapacitors nowadays. Since a satisfactory capacitance can be generated due to the high ionic accessible surface area of the electrode material in a certain electrolyte, carbonaceous materials with the large surface area have been extensively explored over the past two decades (
The main energy storage mechanism of supercapacitors prepared from 3D carbonaceous materials such as ACs and carbon aerogels is EDLCs (
Nevertheless, insufficient energy density still have being an important defect for carbonaceous materials, which shortens the long-term availability of the energy provided by supercapacitors and fall behind practical demands (e.g., in electric vehicles and rail transit) (
Several reviews related with carbonaceous electrode materials have been reported already (
2 Preparation and performance of carbonaceous electrode materials
Many sources of carbonaceous materials. Various natural resources, such as biomass materials, crude oil, nature gas and coal, artificial polymer such as polyvinylidene chloride (PVDC), can be used as precursors for carbonaceous materials. There are various methodologies for converting carbonic precursors into carbonaceous materials, such as physical or chemical vapour deposition, pyrolytic heating as well as organic redox methodologies (
2.1 CQDs and other 0D carbonaceous materials
CQDs are a typical class of 0D carbonaceous materials, which are composed of dispersed, quasi-spherical and ultrafine carbon nanoparticles with an average size below 10 nm (
Application of pure CQDs as electrode materials for supercapacitors has not received much attention. But more and more CQDs based composites show excellent electrochemical performance for supercapacitors. Because of p–p conjugation, functional groups and strong electrostatic interaction of CQDs, a number of molecules such as organic molecules, nanoparticles, and polymers are able to connect to the surface of CQDs. For example,
The diameter of other 0D carbonaceous materials usually larger than 50 nm. Compare with solid nanospheres which have limited electrochemical performances, hollow nanospheres have gained extensive interest. For instance,
2.2 CNTs and other 1D carbonaceous materials
On account of their structural alignment, CNTs can be divided into two groups: single-walled (SWCNTs) and multi-walled carbon nanotubes (MWCNTs). A SWCNT is composed of a cylindrical-shaped graphene sheet with uniphase and outer phase bonds of sp2 carbon atoms (
Carbon nanofibers (CNFs) are another kind of widely studied 1D carbonaceous materials. One of the most common procedure to synthesize CNFs is electrochemical spinning. Tao et al. (2019) synthesized electrospun CNFs based on waste walnut shells via the procedure of liquefying, electrospinning and carbonizing. Singh et al. (2021) obtained self-standing CNFs at different temperatures, they found the 800°C heat treated CNF exhibits largest specific capacitance (196.63 F/g at a current density of 1 A/g).
2.3 Graphenes and other 2D carbonaceous materials
Graphene is like a special kind of graphite, but only a single layer atomic thick. Pure graphene is a carbonaceous material with excellent electrical and thermal conductivity, strong physical strength and good chemical stability. Embed these properties into supercapacitors with good cyclic stability and high power density would be advantageous. Many nanocomposites with heteroatoms or functional groups can be formed based on graphene (Olabi et al., 2021). Wang et al. (2009) prepared graphene materials from graphene oxide sheets that synthesized through modified Hummers’ method (
2.4 Carbon aerogels, CDCs, ACs and other 3D porous carbonaceous materials
Carbon aerogels usually can be obtained from organic aerogel through pyrolysis process. These highly porous carbonaceous materials exhibit good thermal, electrical and mechanical properties, and has greater compressibility and adsorption. Structure and properties of carbon aerogels can be controlled by different preparation methods, which let carbon aerogels become one of potential candidate materials for supercapacitors (Pekala, 1989;
CDCs are a late-model type of porous carbonaceous type of carbon materials obtained through taking carbide as a precursor and trying to remove metal atoms or non-metal atoms in the lattice layer by layer, leaving a skeleton carbonaceous structure (Meng et al., 2004). By adjusting the temperature, atmosphere composition, reaction time and other parameters during the reaction process, nano-scale regulation can be achieved to obtain CDCs coatings with different structures (
ACs are prepared from carbon-containing raw materials through pyrolysis and activation processing. These carbonaceous materials usually have developed pore structures and high surface area (Nizam et al., 2021). Many supercapacitor electrodes based on ACs exhibit excellent performances not only owing to their highly porous structure but also due to their redox behavior (
Carbon foams, which could possess good thermal stability, high mechanical strength, open cell structure, adjustable electrical and thermal conductivities, are mainly prepared via three routes: Compaction and exfoliation of graphite, template carbonization of carbon precursor as well as blowing of carbon precursors such as pitches with subsequent carbonization (
3 Comparisons of different carbonaceous electrode materials
Comparisons of different carbonaceous materials for supercapacitor are listed in Table 1. From the view of industrial production, although aerogel, CDCs, CQDs, CNTs, and graphene materials exihited controllable pore structures, large surface area and high chemical stability, all these materials, which may be good candidates for preparing on-chip microsupercapacitors, require time-consuming, complicated and expensive producing process, which probably hinder their large-scale application. On the other hand, ACs have been reported as the most preferable carbonaceous electrode materials (Wang et al., 2015). To further reduce the cost of industrial production of carbonaceous electrode materials, low cost precursors should be preferred. Carbonaceous wastes such as plastic wastes, agricultural biomass wastes, industrial wastes, medical wastes and municipal wastes have great recycling value. Rational design of chemical processes for converting carbonaceous waste into carbonaceous electrode materials can also reduce potential carbon dioxide emissions (Tatrari et al., 2021). On the other hand, it is essential to probe new methods to further enhance electrochemical performances of carbonaceous electrode materials.
TABLE 1
| Carbonaceous materials | Carbon aerogels | CDCs | Carbon foams and templated carbon | Graphene and graphene derived materials | CQDs, CNTs and their derived materials | ACs |
|---|---|---|---|---|---|---|
| Preparation cost | Medium (M) | M | M | M | High (H) | Low (L) |
| Scalability | M | M | M | M | L | H |
| Conductivity | L | M | M | H | H | L |
| Specific surface area (m2/g) | ≤1,000 | ≤3,500 | ≤4,500 | 2,630 (Theoretical values for graphene) Rashidi and Yusup (2020) | 1,315 (Theoretical values for CNTs) Rashidi and Yusup (2020) | ≤3,000 |
Comparisons of different carbonaceous electrode materials for supercapacitors.
4 Functionalization of carbonaceous electrode materials
The nature of carbonaceous electrode materials can be monitored and adjusted through heteroatom doping and surface functionalization with different methodologies. For instance, the position and performances of surface functional groups can be adjust via thermal heating or chemical treatments. On the other hand, doping of heteroatoms (e.g., O, N, F, S, B, P and metallic atoms into carbon skeleton will often adjust carbonaceous materials’ wettability, electroconductibility and capacitance. As shown in Supplementary Figures S7, S8, those surface functionalization can be either derived from heteroatoms containing precursors or achieved through post-treatment/activation process (Teimuri-Mofrad et al., 2022;
4.1 Functionalization of carbon aerogels
Modification of aerogels is a major trend for carbon aerogels. At present, the modification methods of aerogels mainly include surface modification, doping and composite (
Conventional carbon aerogels based on phenolic resins are expensive and generate toxic pollutants during pyrolysis. Recently, several biomass carbon aerogels have been developed. Biomass resources are usually rich in oxygen and nitrogen elements, these characteristics could be used for self-activation to achieve the effect of self-doping (Mei, 2022). Ping et al. (2016) reported a carbon fiber aerogel based on natural cotton. The specific surface area of these carbon aerogels can be adjusted from 1,536 to 2,436 m2/g via controlling the KOH amount in activation process (Ping et al., 2016). Zhai et al. (2021) reported a series of N self-doped carbon aerogel (NSCA) using chitin as carbon and nitrogen sources through microwave hydrothermal reaction and carbonization with Zinc chloride as the activating and dehydrating agent. NSCA-1000 exhibited 249.4 and 164.9 F/g specific capacitances at the current densities of 1.0 and 10 A/g (Zhai et al., 2021).
4.2 Functionalization of low-dimensional carbonaceous electrode materials
Both CNTs and Graphene are low-dimensional electrode material for supercapacitor. Theoretically, CQ of CNTs graphene maybe improved by suitable functionalization (Mousavi-Khoshdel and Targholi, 2015; Mousavi-Khoshdel et al., 2016; Wang and Pumera, 2016). Silva et al. (2020) employed density functional theory (DFT) calculations and molecular dynamics atomistic simulations to determine CT. Their results exhibited that doped electrodes present variations in CQ which is in the range of 0–200 μF/cm2, because of the changes in the pristine graphene’s electronic structure. However, neither vacancies nor doping atoms has appreciable influence on CD (Silva et al., 2020). Song et al. (2018) explored the CQ of graphene oxide (GO) through DFT calculations. As shown in Supplementary Figure S4, it was found that intoducing oxygen-containing groups can enhance the total density of states near the Fermi level. Moreover, increasing the concentrations of hydroxy and epoxy groups will improve CQ of GO (Song et al., 2018).
Mousavi-Khoshdel M. investigated the impact of doping (P, S, Si) and co-doping (P N, S N, Si N) of graphene on structural parameters, electronic properties as well as CQvia DFT and generalized-gradient approximation (GGA). The obtained results indicated that in comparison with pristine graphene sheets, codoping of graphene generates new electronic states and accumulates larger quantity of electrical charge on co-doped graphene sheets, which will enhance their quantum capacitance consequently (Morteza et al., 2015). As shown in the Supplementary Figure S5,
Numerous reported experimental studies also demonstrated that functionalizing graphene and carbon nanotubes can effectively improve their electrochemical performances. Song et al. (2021c) synthesized N-doped graphene sheets (NGS) through a solid-state microwave-mediated process. Subsequently, experimental electrodes employing NGS were fabricated. At 0.5 A/g current density, the electrode’s specific capacitance reached 208.17 F/g (Song et al., 2021c). Vermisoglou et al. (2021) utilized fluorographene, which was uniformly linked with amino acid moieties on graphene’s both sides. By adding non-toxic pore formers and adjusting conditions of reactions, the hierarchical porosity and optimal degree of functionalization were achieved. At 0.25 A/g current density, this material exhibited high capacitance of about 390 F/g. The assembled supercapacitor device was tested for 30,000 cycles of charge-discharge at a current density of 2 A/g, showing 82.3% capacitance retention (Vermisoglou et al., 2021). Tong et al. (2021) synthesized poly-3,4-ethylenedioxythiophene (PEDOT) on graphene nanosheet-deposited open-pored polyurethane (PU) sponge by vapor-phase polymerization (VPP) way to prepare porous electrodes. Under 0.1 mA/cm2 current density, the obtained electrodes showed high areal specific capacitance of 798.2 mF/cm2 (Tong et al., 2021).
4.3 Functionalization of ACs
Hydrophobic nature of unmodified ACs coursed weak infiltration of electrolyte to electrode, and ion-accessible surface limitation (Zhang et al., 2019). Zhai et al. (2011) concluded that porous structure, conductivity and surface properties optimization are required to ensure maximum capacitance of ACs. Functionalization of ACs as supercapacitor electrode materials has attracted more and more attentions nowadays (Rashidi and Yusup, 2020) Yang and Zhou (2017) reported N atoms inclusion into the structure of ACs to provide an extra redox reaction for pseudocapacitor.
5 Summary and future perspectives
This review proposes a brief description about the operating principle and evaluation parameters for supercapacitor. Since both EDLCs and pseudocapacitors occur on surface electrodes, carbonaceous electrode materials’ surface strongly affect the electrochemical performances of supercapacitor, which could be further improved through heteroatom doping and surface functionalization. Theoretically, CQ of CNTs and graphene could be improved via heteroatom doping, which were demonstrated by experimental studies. As a major trend for carbon aerogels and ACs, surface modification, doping and composite can not only improve their optimization of pore size and structure, conductivity and surface properties, but also introduce extra pseudocapacitance to these materials.
Different carbonaceous materials were roughly classified and their preparation process and properties was discussed briefly. Compared with other carbonaceous materials, ACs and aerogels from biomass have drawn more and more attention nowadays owing to its inexpensive cost and renewablity. Especially, the production and utilization of domestic, medical and industrial wastes residues derived carbonaceous materials should be of great significance for controlling environmental pollution and reducing CO2 emissions, which we think will be worth to further studies.
Articles on the manufacturing technology and equipments for carbonaceous materials are relatively rare. Moreover, articles discussed waste gas composition and disposal methods in different carbon material industrialization processes (carbonization, activation) are very few. Which we think should be further study in future.
Statements
Author contributions
Conceptualization, YL and JW; methodology, XH and XS; investigation, DJ and SZ; writing-original draft preparation, YL, JL, and YZ; writing-review and editing, YL and JW; supervision,YL and XS; funding acquisition, YL, XS, and YZ. All authors contributed significantly to the manuscript and have read and agreed to the published version of the manuscript.
Funding
The authors thank Project of Zhejiang Provincial Department of Education (No. Y202043207), Science and Technology Project of Zhejiang Province (No.2022C01182) and Zhejiang Provincial Natural Science Foundation of China (No. LY19B010003) for supporting.
Conflict of interest
JL was employed by Hangzhou Plastics Industry Co., LTD.
The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Publisher’s note
All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.
Supplementary material
The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/fenrg.2022.957032/full#supplementary-material
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Summary
Keywords
supercapacitors, electrode materials, surface functionalization, working principal, EDLC
Citation
Lv Y, Wang J, Ji D, Li J, Zhao S, Zhao Y, Cai Z, He X and Sun X (2023) Carbonaceous electrode materials for supercapacitor: Preparation and surface functionalization. Front. Energy Res. 10:957032. doi: 10.3389/fenrg.2022.957032
Received
30 May 2022
Accepted
28 November 2022
Published
26 January 2023
Volume
10 - 2022
Edited by
Hongyuan Zhao, Henan Institute of Science and Technology, China
Reviewed by
Subramania Angaiah, Pondicherry University, India
Mert Akin, Farasis Energy, United States
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© 2023 Lv, Wang, Ji, Li, Zhao, Zhao, Cai, He and Sun.
This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
*Correspondence: Yaokang Lv, yaokanglv@zjut.edu.cn; Xuehua He, hzhexh@zjut.edu.cn; Xiaofang Sun, zgdsxf@zjut.edu.cn
This article was submitted to Electrochemical Energy Conversion and Storage, a section of the journal Frontiers in Energy Research
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