Abstract
Recently, our modern society demands the portable electronic devices such as mobile phones, laptops, smart watches, etc. Such devices demand light weight, flexible, and low-cost energy storage systems. Among different energy storage systems, supercapacitor has been considered as one of the most potential energy storage systems. This has several significant merits such as high power density, light weight, eco-friendly, etc. The electrode material is the important part of the supercapacitor. Recent studies have shown that there are many new advancement in electrode materials for supercapacitors. In this review, we focused on the recent advancements in the cobalt oxides, manganese oxides, and their composites as an electrode material for supercapacitor.
Introduction
Energy storage has an equal importance as energy production. To face the global challenges, recently, our modern society demands lightweight, flexible, inexpensive, and environmentally friendly energy storage systems (Meng et al., 2010; Chodankar et al., 2015). Battery and supercapacitor are the major energy storage devices. But, slow charge–discharge rate, short life cycles, and high weight of battery limit its applications in portable and wearable devises (Meng et al., 2010). At present, supercapacitors have been receiving a great attention, because of their important features such as high energy density, high power density, light weight, fast charging–discharging rate, secure operation, and long life span (Jayalakshmi and Balasubramanian, 2008; Chodankar et al., 2015). The supercapacitor is also called electrochemical capacitor. This is used in various applications such as hybrid vehicles, power backup, military services, and portable electronic devises like laptops, mobile phones, wrist watches, wearable devised, roll-up displays electronic papers, etc. (Lee et al., 2011; Wang et al., 2012).
Classification of the Supercapacitor
On the basis of charge storage mechanism and material used as the electrode, the supercapacitors are divided into two categories: electrochemical double layer supercapacitors (EDLCs) and pseudocapacitor (Jayalakshmi and Balasubramanian, 2008). In EDLCs, the specific capacitance arises from the non-Faradaic charge storage mechanism between electrode and electrolyte interface (Jayalakshmi and Balasubramanian, 2008; Wang et al., 2012). The materials that have been used as electrode for EDLCs are porous carbon (Kang et al., 2015), SWNT (Liu et al., 2006), MWNT (Huang et al., 2014a), reduce graphine oxide (Zhang and Zhao, 2012), aerogel (Faraji and Ani, 2015), etc. In pseudocapacitor, the specific capacitance arises from Faradaic reaction at the electrode interface. The materials that have been studied as electrode for pseudocapacitors are transition metal oxides and conducting polymers (Wang et al., 2012).
In particular, the specific capacitance of the supercapacitors depends on the surface area and the pore size distribution of the electrode material. Compared with the transition metal oxides and conducting polymers, carbon and its different types have high surface area (3.270 m2g−1) (Kang et al., 2015). However, this high surface area of carbon is not completely accessible for the electrolyte (Faraji and Ani, 2015). To overcome this shortcoming, the composites of carbon with transition metal oxides or conducting polymer have received great attention. These composite are also called hybrid materials. The use of hybrid material as an electrode in supercapacitors result in the third category of supercapacitors called hybrid supercapacitors. In hybrid supercapacitors, the specific capacitance arises from Faradic as well as non-Faradic charge storage mechanism at the electrode and electrolyte interface (Zhang et al., 2013; Pardieu et al., 2015).
Parameters for Supercapacitor
The specific capacitance (Cs) (Fg−1), energy density E (Wh kg−1), power density P (kW kg−1), and retention capacity or coulomb efficiency (η) are the crucial characteristics of the supercapacitor device. The (Cs) (Fg−1) at the single electrode of the device is calculated given by, where m is the mass (g cm−1) deposited, I(v) is the response current (mA) of the electrode material for unit area, V is the scan rate, Vc−Va is the operational potential window in (V), Va anodic current, and Vc cathodic current. Energy density E (Wh kg−1) and power density P (W kg−1) of supercapacitor are calculated using following relations as, where Cs is specific capacitance (Fg−1), Vmax and Vmin are the maximum and minimum voltage achieved during charging and discharging process, respectively, in volt (V), and tD is the discharging time (s) for a cycle of the supercapacitor. The retention of specific capacitance is calculated using the relation, where tC and tD are the charge and discharge time (s), respectively, for a cycle of the supercapacitor (Wang et al., 2010; Dubal et al., 2012).
Recent Advances in Cobalt Oxide Supercapacitor
The transition metal oxides have a great scientific significance. These are the basis of a variety of functional materials (Shinde et al., 2015). Among the various supercapacitor electrode materials, transition metal oxides offer high electronegativity, rich redox reactions, low cost, environmental friendliness, and excellent electrochemical performance. Different transition-metal oxides, such as IrO2, RuO2, Co3O4, MnO2, Fe2O3, SnO2, NiO, etc., have been extensively studied as the electrode material for supercapacitor (Luo et al., 2014). Among these, RuO2 has been identified as a dominant candidate because it has high theoretical specific capacitance (1,358 Fg−1), high electrical conductivity (300 S cm−1), and high electrochemical stability (Yu et al., 2013). However, the high cost and toxicity associated with the RuO2 limits its commercial applications (Deng et al., 2014).
Furthermore, the cobalt oxides have received significant interest in recent years because of their low cost, non-toxic, easy synthesis, and environmental friendly nature. The cobalt oxides have high theoretical capacitance (CoO: 4.292 Fg−1, Co2O4: 3.560 Fg−1) (Cheng et al., 2010; He et al., 2012). Additionally, cobalt oxides show excellent electrochemical behavior in alkaline as well as organic electrolyte. These have the ability to interact with the ions of the electrolyte at the surface as well as through the bulk of the material (Vijayakumar et al., 2013). The features of cobalt oxides such as morphology, structures, and dimension can be easily controlled via adjusting the preparative parameters such as, reaction temperature, reaction time, concentration of matrix solution, complexing agent, etc. (Wei et al., 2015a).
An optimize microstructure and controlled morphology of the material will enhance the specific surface area and pore size distribution, which facilitate the electrolyte ion transport in the material (Meher and Rao, 2011). Recently, many new approaches have been successfully in use to synthesize the meso and microporous nanostructure cobalt oxide materials such as hydrothermal method (Meher and Rao, 2011), chemical bath deposition method (Xu et al., 2010), hydrothermal precipitation method (Yu et al., 2009), solvothermal synthesis method (Yang et al., 2013), combustion synthesis method (Deng et al., 2014), microwave-assisted synthesis method (Vijayakumar et al., 2013), etc.
The specific capacitance of the cobalt oxide strongly depends on morphology, surface area, and pore size distribution. Recently, use of new synthesis approaches, surface modifying agents, complexing, and structure directing agent results in high-specific capacitance, which is equal the theoretical specific capacitance cobalt oxide. In this review paper, we have focused the recent advancements in the cobalt oxides and their composites as the electrode material. Table 1 shows the preparation and supercapacitive performance of cobalt oxide and their composites based supercapacitors.
Table 1
| Sr. no. | Material | Method of synthesis | High surface area | Electrolyte | High Sp. capacitance | Retention | Year | Reference |
|---|---|---|---|---|---|---|---|---|
| 1 | Co2O3 on NiO substrate | Electrodeposition method | 1 M KOH | 345 Fg−1 at 20 mV s−1 | >50% after 200 | 2014 | Sarma et al. (2014) | |
| 2 | Co3O4-decorated graphene | Microwave-assisted method | – | 1 M KOH | 600 Fg−1 at 0.7 A g−1 | 94.5% after 5,000 cycles | 2015 | Kumar et al. (2015) |
| 3 | Pongam seed shell-derived activated carbon and cobalt oxide (Co3O4) nanocomposite | KOH activation method | 164 m2 g−1 | 1 M KOH electrolyte | 94 Fg−1 at 1 A g−1 | 88% after 1,000 cycles | 2015 | Madhu et al. (2015) |
| 4 | Co3O4/NiCo3O4 double-shelled nanocages | The facile synthesis | – | 2 M KOH | 972 Fg−1 at a current density of 5 A g−1 | 92.5% after 12,000 cycles | 2015 | Hu et al. (2015) |
| 5 | Synthesized titania nanotube cobalt (CoS) sulfide composite | Electrodeposition method | – | 1 M Na2SO3 | 400 Fg−1 at charge density 5 mA cm−2 | >80% after 1,000 cycles | 2015 | Ray et al. (2015) |
| 6 | Co3O4 nanotubes | Chemical deposition method | 6 ML−1 KOH | 574 Fg−1 at 0.1 A g−1 | 95% after 1,000 cycles | 2010 | Xu et al. (2010) | |
| 7 | Ultrafine Co3O4 nanocrystal electrode | Laser ablation in liquid method | – | 177 Fg−1 at scan rate 1 mV s−1 | 100% after 20,000 cycles | 2016 | Liu et al. (2016) | |
| 8 | Cobalt tungstate (CoWO4) | Chemical precipitation reaction | – | 0.2 M H2SO4 | 378 Fg−1 at scan rate 2 mV s−1 | 95.5% after 4,000 cycles | 2016 | Adib et al. (2016) |
Co3O4-based supercapacitors.
Recent Advances in Manganese Oxide Supercapacitor
Manganese (Mn) has different oxidation states. Out of these, the most stable oxidation states are Mn (II) and Mn (IV). The Mn (II) forms MnO, on the other hand, Mn (IV) forms MnO2 and Mn2O3. The MnO2 has α, β, γ, and δ -type polymorph (Chen et al., 2014; Salunkhe et al., 2015). The advantages of manganese-based metal oxides include low cost, low toxicity, natural abundance, and environmental friendly in nature (Sui et al., 2015; Wei et al., 2015b). In aqueous and organic electrolyte, the MnO, MnO2, and Mn2O3 can form the different oxidation states. Thus, it results in the high-specific capacitance. The highest reported theoretical specific capacitance of MnO2 is 1.370 Fg−1 (Guo et al., 2015a; Wei et al., 2015b). However, the low electrical conductivity and large volume change during the charge–discharge process result in the unsatisfactory rate performance and cyclic stability. In consequence, this reduces the specific capacitance of the manganese oxides-based supercapacitors (Cabana et al., 2010; Chen et al., 2010). To overcome such hindrances, recently, the researchers have been executing many new strategies, such as use of carbon containing materials for increasing the electrical conductivity and adopt the volume buffers for relaxing internal stresses (Yao et al., 2008; Sui et al., 2015). Manganese oxides have been prepared by various synthesis methods, such as pulse laser deposition method (Xia et al., 2011), hydrothermal method (Zhang et al., 2014), electrochemical synthesis method (Jiang and Kucernak, 2002), redox deposition method (Bordjiba and Bélanger, 2009), successive hydrolysis–condensation method (Sawangphruk and Limtrakul, 2012), etc. Further, the detail of MnO2 synthesis and their supercapacitive performance are shown in Table 2.
Table 2
| Sr. no. | Material | Method of synthesis | High surface area | Electrolyte | High Sp. capacitance | Retention | Year | Reference |
|---|---|---|---|---|---|---|---|---|
| 1 | Manganese oxide (MnO2)/three-dimensional (3D) reduced graphene oxide (RGO) | Reverse microemulsion (water/oil) method | 142 m2 g−1 | 0.1 M Na2SO4 | 709.8 Fg−1 at 0.2 A g−1 | 97.6% after 1,000 cycles | 2015 | Wei et al. (2015b) |
| 2 | Coaxial mesoporous MnO2/amorphous-carbon nanotubes | Redox reaction between KMnO4 and amorphous carbon nanotube in acid solution | – | 1 M Na2SO4 | 362 Fg−1 at the current density of 0.5 A g−1 | 88.6% after 3,000 cycles | 2015 | Zhu et al. (2015) |
| 3 | 3D porous CNT/MnO2 composite | Dipping and drying process followed by a potentionstatic deposition technology | 230.85 m2 g−1 | 0.5 M NaOH | 160.5 Fg−1 at the current density of 1 A−1 | – | 2015 | Guo et al. (2015b) |
| 4 | Carbon nanosheets supported MnO2 | Carbonization and reduction method | 573 m2 g−1 | 6 M KOH | 656 Fg−1 at a current density of 1 A g−1 | 80% after 5,000 cycles | 2015 | Sun et al. (2015) |
| 5 | A RGO/manganese dioxide (MnO2)/silver nanowire ternary hybrid film | A facile vacuum filtration and subsequent thermal reduction | – | 0.5 M Na2SO4 | 4.42 F cm−3 at a scan rate of 10 mV s−1 | 90.3% after 6,000 cycles | 2015 | Liu et al. (2015) |
| 6 | Three-dimensional carbon nanotubes@MnO2 core shell nanostructures | A floating catalyst chemical vapor deposition process and a facile hydrothermal approach | 127.5 m2 g−1 | 1 M Na2SO4 | 325.5 F g−1 at a current density of 0.3 A g−1 | 90.5% after 5,000 cycles | 2014 | Huang et al. (2014b) |
| 7 | MnO2/Graphine argogel composites | Graphene aerogels: an organic sol-gel process and MnO2 electrochemically deposit on GA | 793 m2 g−1 | 0.5 M Na2SO4 | 410 Fg−1 at 2 mV s−1 | 95% after 50,000 cycles at 1,000 mV s−1 | 2014 | Wang et al. (2014) |
| 8 | Manganese oxide nanosheets/nanoporous gold | Galvanostatic electrodepositon | – | 1 M Na2SO4 | 775 Fg−1 at 1 A g−1 | 95% after 1,000 cycles | 2015 | Zeng et al. (2015) |
| 9 | MnO2 on graphene | Hydrothermal method | – | 1 M Na2SO4 | 315 Fg−1 at a current density of 0.2 A g−1 | 87% retained after 2,000 cycles at 3 A g−1 | 2013 | Liu et al. (2013) |
| 10 | MnO2 nanosheets on flexible carbon fiber cloth | Flexible carbon fiber cloth: the direct carbonization of flax textile redox reaction between carbon and KMnO4 | 33.6 m2 g−1 | 0.1 M Na2SO4 | 683.73 Fg−1 at 2 A g−1 | 94.5% retained after 2,000 cycles | 2015 | He and Chen (2015) |
MnO2-based supercapacitor.
Conclusion and Future Prospective
Recently, cobalt- and manganese-based metal oxide as the electrode materials for supercapacitor have been receiving the great attention. From the recent reports, it has concluded that,
- (1)
Advanced chemical method such as hydrothermal, pulse laser deposition, reverse microemulsion, microwave-assisted, etc., has been assisted to synthesize cobalt- and manganese-based metal oxide material.
- (2)
The specific capacitance of the cobalt oxide- and manganese-based metal oxide supercapacitor strongly depends on morphology, surface area, and pore-size distribution.
- (3)
In most of the reports, the composites of cobalt oxide or manganese oxide with carbon material, i.e., hybrid materials are used as an electrode for supercapacitor. Moreover, this results in high-specific capacitance.
- (4)
In addition, the increase in conductivity of the cobalt oxide and manganese oxides is projected if this material and carbon material are combined. This makes the application of cobalt oxide and manganese oxides in high energy applications. As a result, the proposed material cobalt oxides and manganese oxide are a promising material for flexible, portable high-rate hybrid supercapacitor, and has plenty room for advancements.
Statements
Author contributions
All authors listed have made a substantial, direct, and intellectual contribution to the work and approved it for publication.
Funding
This work is financially supported by University Grant Commission (UGC) New Delhi, India under Minor Research Project (File No.47-763/13/WRO).
Conflict of interest
The 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.
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Summary
Keywords
hybrid supercapacitor, cobalt oxide, manganese oxide, specific capacitance, specific surface area
Citation
Uke SJ, Akhare VP, Bambole DR, Bodade AB and Chaudhari GN (2017) Recent Advancements in the Cobalt Oxides, Manganese Oxides, and Their Composite As an Electrode Material for Supercapacitor: A Review. Front. Mater. 4:21. doi: 10.3389/fmats.2017.00021
Received
10 February 2017
Accepted
30 June 2017
Published
02 August 2017
Volume
4 - 2017
Edited by
Sravendra Rana, University of Petroleum and Energy Studies, India
Reviewed by
Zhengjun Zhang, Tsinghua University, China; Hongchang Pang, Dalian University of Technology (DUT), China
Updates
Copyright
© 2017 Uke, Akhare, Bambole, Bodade and Chaudhari.
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) or licensor 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: Santosh J. Uke, santosh_uke@rediffmail.com
Specialty section: This article was submitted to Nanoenergy Technologies and Materials, a section of the journal Frontiers in Materials
Disclaimer
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