You're using an outdated browser. Please upgrade to a modern browser for the best experience.
MXene/Ferrite Electrode for Supercapacitor Applications: History
View Latest Version
Please note this is an old version of this entry, which may differ significantly from the current revision.

MXene has been identified as a new emerging material for various applications including energy storage, electronics, and bio-related due to its wider physicochemical characteristics. Further the formation of hybrid composites of MXene with other materials makes them interesting to utilize in multifunctional applications. The selection of magnetic nanomaterials for the formation of nanocomposite with MXene would be interesting for the utilization of magnetic characteristics along with MXene. However, the selection of the magnetic nanomaterials is important, as the magnetic characteristics of the ferrites vary with the stoichiometric composition of metal ions, particle shape and size. The selection of the electrolyte is also important for electrochemical energy storage applications, as the electrolyte could influence the electrochemical performance. Further, the external magnetic field also could influence the electrochemical performance.

  • MXene
  • ferrites
  • supercapacitor applications

1. Introduction

MXene, a class of 2D transition metal carbides/nitrides, has been identified as a new emerging material for various applications including energy storage, electronics, and bio-related due to its wider physical characteristics. Further, the formation of hybrid composites of MXene with other materials introduces interesting uses in multifunctional applications. MXene offers tremendous promise for energy storage applications, due to its lamellar construction, outstanding density, conductivity, configurable terminations, and ionic pseudocapacitance charge storage process [1][2][3]. A wide variety of MXenes are produced by diverse mixtures of transition metals, carbon and/or nitrogen, and diverse n layers; however, only a few have been generated and employed in energy storage applications thus far, with Ti3C2Tx being the most investigated [4][5][6][7][8][9]. By removing the A layers from the MAX phase, MXenes are created. The compound is recognized as MXene due to its composition, which is Mn+1AXn, where M is an initial transition metal, A is primarily an element from group IIIA or IVA (i.e., 13 or 14), X is C and/or N, and n is either 1, 2, or 3. MXenes represent a new large family that extends the world of 2D materials, and there has been an increase in interest in 2D materials other than graphene. Distinctive morphologies, strong electronic conductivities, and diverse chemistries, among other distinctive features of MXenes, have made them desirable in numerous applications, particularly for energy storage [10]. Due to its renowned etching processes and the extensive theoretical and experimental investigations on its physicochemical and electrochemical characteristics, Ti3C2Tx, one prominent example among the MXene group, is a key interest of many. The electrochemical characteristics of MXene have been debated in recent years with some experimental evidence [3][6][11][12][13]. In aqueous electrolytes, hydrated cations are intercalated into MXene electrodes. Within the constrained potential window, the hydrated cations establish an electric double layer throughout the interlayer region to provide a standard capacitance. When nonaqueous electrolytes are utilized, the limited solvation shell must progressively breakdown due to the significant internal potential difference in the interlayer, even when solvated ions are diffused into the interlayer during the early phase of charging. Desolvated ions only intercalate when charged more, and a donor band is formed when the desolvated cations’ atomic orbitals cross over with those of MXene. By the charge transition from the metal ions to MXene, the reduction of MXene caused by the donor band development results in an intercalation pseudocapacitance. The detailed charge storage mechanism was explored by a few recent studies [3][13][14][15]. Further the improvement in the charge storage capacity could be enhanced through the surface modification process [16].
Spinel ferrites are homogeneous substances that have the typical chemical form of AB2O4, where A and B are metallic ions that are located at 2 distinct crystallographic places, tetrahedral (A sites) and octahedral (B sites), respectively, with key elements of Fe3+ in their structure. Three distinct spinel ferrite configurations, termed as normal, inverse, and mixed systems, are attainable for the composition of MFe2O4, based on the position of M2+ and Fe3+ location selection. M2+ is distributed at the tetrahedral location and Fe3+ at the octahedral location in a typical spinel configuration of ferrite. Fe3+ is evenly located at both positions in an inverse spinel configuration, whereas M2+ solely resides at the octahedral location. Both ions are indiscriminately located at the tetrahedral and octahedral positions in a mixed spinel configuration. Fe3O4 is considered an intriguing material for energy storage systems due to additional benefits such as high theoretical-specific capacitance (2299 F/g), a wide potential window (−1.2 to 0.25 V), abundance in nature, relative inexpensiveness, lesser toxicity, etc., [17]. The charge storage mechanism in various ferrites was thoroughly analyzed by various experimental methods in supercapacitor applications [17][18][19][20]. All these kinds of ferrite could be easily prepared by selecting suitable precursors for suitable experimental procedures.
The MXene/Ferrite composites have attracted much attention in various applications including batteries, electrochemical supercapacitors, photocatalytic degradation, electromagnetic shield, and water purification methods [21][22][23][24][25][26][27]. The charge storing capacity of various MXenes and ferrites was not achieved towards its theoretical capacity. There are many ongoing investigations focused on improvement in the electrochemical performance of different MXenes, as well as on the various ferrites by adjusting the shape, size, and functional groups. The formation hybrid materials could be advantageous to achieve better outcomes from both materials due to the synergic effect.
The advantages of these magnetic nanocomposites over other available nanocomposites are its magnetic characteristics. These magnetic nanocomposites can be reused after the completion of any specific application. The collection processes of the magnetic nanocomposites are also easy to process with the external magnet because of the magnetic nature of the nanocomposites. Another advantage in this magnetic nanocomposite is the utilization of the eternal magnetic field during the application process. The presence of the external magnetic field with the magnetic nanocomposite definitely could influence the reaction mechanism, which could reflect in the efficiency of the nanocomposites in specific applications [28]. Green synthesis methods are also possible in the formation of these kinds of composites to obtain environmental sustainability. The effect of the external magnetic field on a few ferrites and non-magnetic materials has been studied. However, the optimization of external field strength for various magnetic and non-magnetic materials is much needed. The composite of MXene with ferrites requires attention as there are many opportunities to explore more nanocompositions.

2. MXene/Ferrite Electrode for Supercapacitor Applications

The utilization of multivalence metal ions in the mixed ferrite could be beneficial for the charge transfer process during electrochemical reactions. In this regard, Co-ferrite (CoFe2O4) has been attempted for the formation of nanocomposites with MXene due to the extraordinary theoretical specific capacitance, mixed valence, and chemical stability [22]. Co-ferrite is an established example of an inverse spinel in which Fe+3 ions coexist with Co+2 ions at tetrahedral regions and Fe3+ ions at octahedral regions, resulting in enhanced redox activity and effective charge storage. The main issue with the Co-ferrite in supercapacitor applications is its low electronic conductivity. However, this could be solved by forming hybrid composites with other materials that have excellent electronic conductivity. The addition of Co-ferrite would be advantageous in MXene/Co-ferrite nanocomposites, as the Co-ferrite could be used to avoid the restacking of MXene layers. Co-precipitation with wet chemical etching processes were utilized for the formation of Co-ferrite and MXene. The MXene/Co-ferrite composite formation was achieved through the ultra-sonication process for one hour and dried at 80 °C in vacuum. The single phase of Co-Ferrite was evidenced for bare Co-ferrite nanoparticles as well as for the MXene/Co-ferrite nanocomposite, and the observed XRD pattern of bare Co-ferrite and MXene/Co-ferrite are shown in Figure 1i(a,b). The characteristics reflections of MXene were not witnessed in the XRD pattern of MXene/Co-ferrite nanocomposite. However, the presence of MXene in the MXene/Co-ferrite nanocomposite was discussed through the observation if peak broadening occurs, variation in the lattice parameters and shift in the characteristic peak is observed. The observed peak broadening and peak shift are shown in Figure 1i(c,d). The SEM micrograph confirms the Co-ferrite nanoparticles sizes ranging from 70–90 nm and the layers construction of MXene as shown in Figure 1ii(a–c). The uniform dispersion of Co-ferrite over the MXene layered structure was evidenced from the SEM micrograph as shown in Figure 1ii(d). It is also noted that the Co-ferrite nanoparticles were also incorporated between MXene layers, which would be advantageous for the supercapacitor applications.
Figure 1. (i) XRD pattern of (a) Co ferrite, (b) MXene/Co-ferrite, (c) comparison pattern, and (d) magnified at lower angle, and (ii) SEM micrograph of (a,b) Co-ferrite, (c) MXene and (d) MXene/Co-ferrite nanocomposite. Reproduced with permission from [22] Copyright (2020) American Chemical Society.
The average layer thickness was estimated as 1 nm from atomic force microscopic experiments. The electrochemical supercapacitor analysis of the individual and nanocomposites were assessed in 1 M KOH electrolyte in a potential window of 0.0 to 0.5 V. The cyclic voltammogram curve shows the two distinct anodic and cathodic points, which might be due to the transition of Fe2+/Fe3+ and Co2+/Co3+ during the electrochemical redox reactions. The overall electrochemical reactions with the MXene/Co-ferrite nanocomposite were explained thorough the following reactions,
CoFe2O4+H2O+OH2 FeOOH+CoOOH+e
(1)
CoOOH+OH CoO2+H2O+e
(2)
FeOOH+H2O FeOH3 FeO42+3e
(3)
The better electrochemical super capacitive performance was observed for MXene/Co-ferrite compared with bare Co-ferrite and MXene. The detailed electrochemical studies were carried out for the MXene/Co-ferrite nanocomposites. The CV curves were measured at the scan rate of 10 to 100 mV/s and the measured CV curves are shown in Figure 2a. The charge/discharge curves were measured at the current density of 1 to 8 A/g and the observed curves are shown in Figure 2b. The specific capacitance was estimated from the Galvanostatic charge-discharge (GCD) curves and calculated Cs values corresponding to its current densities are shown in Figure 2c. The highest Cs value of 1268 F/g was achieved at a current density of 1 A/g., whereas, with the same current density, bare Co-ferrite and MXene showed a specific capacitance value of 594 and 1046 F/g, respectively. The long-term cyclic stability was evidenced up to 5000 cycles with a current density of 7 A/g, and the stability curve is shown in Figure 2d. The calculated specific capacity corresponding to its current densities is shown in Figure 2e. The highest specific capacity value of 440 C/g at a current density of 1 A/g was achieved with the lower charging transfer resistance values of 0.25 Ω.
Figure 2. (a) CV, (b) GCD curves, (c) Cs vs. current density, (d) cyclic stability and (e) specific capacity vs. current density. Reproduced with permission from [22] Copyright (2020) American Chemical Society.
The observed electrochemical super capacitive characteristics of MXene/Co-ferrite indicate that these kinds of composites could be further investigated for the improvement in the specific capacitance and cyclic stability.
A recent study shows that the selection of electrolyte is also important for the MXene based ferrite composites [29]. The bare Fe3O4 and MXene/ Fe3O4 magnetic nanocomposites were developed through the modified chemical oxidation process by optimized experimental conditions. A few µm-sized MXenes and particle sizes ranging from 80 to 160 nm of Fe3O4 were evidenced from the microscopic measurements. The attachment of Fe3O4 on the MXene sheets in the MXene/Fe3O4 nanocomposite was evidenced from the TEM micrograph as shown in Figure 3.
Figure 3. TEM Micrograph of (a) MXene, and (b) MXene/ Fe3O4.
Three electrolytes of LiCl, KOH and Na2SO4 were used to evaluate the suitable electrolyte for MXene/Ferrite composites with reduced graphene oxide. The measured CV, GCD curve are shown in Figure 4a,b. The higher area was observed for the nanocomposites characterized in LiCl electrolyte. Also, the LiCl showed better charge/discharge characteristics for MXene/Fe3O4 nanocomposite, compared with other two electrolytes. The estimated Cs with various current densities is shown in Figure 4c along with the EIS spectra in Figure 4d. The observed electrochemical performance demonstrated that the LiCl could provide better performance, which might be due a better combination of the lowest Li ion with the higher pore sizes in the MXene/ferrite composites. However, this electrolyte needs to be evaluated for other various combinations of MXene/ferrites to generalize the electrolyte characteristics.
Figure 4. (a) CV, (b) GCD, (c) Cs vs. current density, and (d) EIS curves of MXene/Fe3O4.

This entry is adapted from the peer-reviewed paper 10.3390/mi13101792

References

  1. Chen, Y.; Yang, H.; Han, Z.; Bo, Z.; Yan, J.; Cen, K.; Ostrikov, K.K. MXene-Based Electrodes for Supercapacitor Energy Storage. Energy Fuels 2022, 36, 2390–2406.
  2. Zhan, C.; Naguib, M.; Lukatskaya, M.; Kent, P.R.C.; Gogotsi, Y.; Jiang, D.E. Understanding the MXene Pseudocapacitance. J. Phys. Chem. Lett. 2018, 9, 1223–1228.
  3. Okubo, M.; Sugahara, A.; Kajiyama, S.; Yamada, A. MXene as a Charge Storage Host. Acc. Chem. Res. 2018, 51, 591–599.
  4. Gogotsi, Y.; Anasori, B. The Rise of MXenes. ACS Nano 2019, 13, 8491–8494.
  5. Naguib, M.; Mochalin, V.N.; Barsoum, M.W.; Gogotsi, Y. 25th Anniversary Article: MXenes: A New Family of Two-Dimensional Materials. Adv. Mater. 2014, 26, 992–1005.
  6. Mu, X.; Wang, D.; Du, F.; Chen, G.; Wang, C.; Wei, Y.; Gogotsi, Y.; Gao, Y.; Dall’Agnese, Y. Revealing the Pseudo-Intercalation Charge Storage Mechanism of MXenes in Acidic Electrolyte. Adv. Funct. Mater. 2019, 29, 1902953.
  7. Anasori, B.; Lukatskaya, M.R.; Gogotsi, Y. 2D Metal Carbides and Nitrides (MXenes) for Energy Storage. Nat. Rev. Mater. 2017, 2, 16098.
  8. Ling, Z.; Ren, C.E.; Zhao, M.Q.; Yang, J.; Giammarco, J.M.; Qiu, J.; Barsoum, M.W.; Gogotsi, Y. Flexible and Conductive MXene Films and Nanocomposites with High Capacitance. Proc. Natl. Acad. Sci. USA 2014, 111, 16676–16681.
  9. Kurra, N.; Ahmed, B.; Gogotsi, Y.; Alshareef, H.N. MXene-on-Paper Coplanar Microsupercapacitors. Adv. Energy Mater. 2016, 6, 1601372.
  10. Ghidiu, M.; Naguib, M.; Shi, C.; Mashtalir, O.; Pan, L.M.; Zhang, B.; Yang, J.; Gogotsi, Y.; Billinge, S.J.L.; Barsoum, M.W. Synthesis and Characterization of Two-Dimensional Nb4C3 (MXene). Chem. Commun. 2014, 50, 9517–9520.
  11. Zhu, Q.; Li, J.; Simon, P.; Xu, B. Two-Dimensional MXenes for Electrochemical Capacitor Applications: Progress, Challenges and Perspectives. Energy Storage Mater. 2021, 35, 630–660.
  12. Das, P.; Wu, Z.S. MXene for Energy Storage: Present Status and Future Perspectives. J. Phys. Energy 2020, 2, 032004.
  13. Ando, Y.; Okubo, M.; Yamada, A.; Otani, M. Capacitive versus Pseudocapacitive Storage in MXene. Adv. Funct. Mater. 2020, 30, 2000820.
  14. Xu, J.; Hu, X.; Wang, X.; Wang, X.; Ju, Y.; Ge, S.; Lu, X.; Ding, J.; Yuan, N.; Gogotsi, Y. Low-Temperature Pseudocapacitive Energy Storage in Ti3C2Tx MXene. Energy Storage Mater. 2020, 33, 382–389.
  15. Wang, T.; Zhao, J.; Qi, L.; Li, G.; Yang, W.; Li, Y. Ultrathin Graphdiyne Oxide-Intercalated MXene: A New Heterostructure with Interfacial Synergistic Effect for High Performance Lithium-Ion Storage. Energy Storage Mater. 2023, 54, 10–19.
  16. Li, J.; Yuan, X.; Lin, C.; Yang, Y.; Xu, L.; Du, X.; Xie, J.; Lin, J.; Sun, J. Achieving High Pseudocapacitance of 2D Titanium Carbide (MXene) by Cation Intercalation and Surface Modification. Adv. Energy Mater. 2017, 7, 1602725.
  17. Nithya, V.D.; Sabari Arul, N. Progress and Development of Fe3O4 Electrodes for Supercapacitors. J. Mater. Chem. A 2016, 4, 10767–10778.
  18. Arun, T.; Kavin Kumar, T.; Udayabhaskar, R.; Morel, M.J.; Rajesh, G.; Mangalaraja, R.V.; Akbari-Fakhrabadi, A. Size Dependent Magnetic and Capacitive Performance of MnFe2O4 Magnetic Nanoparticles. Mater. Lett. 2020, 276, 128240.
  19. Nwodo, M.O.; Obodo, R.M.; Nwanya, A.C.; Ekwealor, A.B.C.; Ezema, F.I. Recent Developments in Metal Ferrite Materials for Supercapacitor Applications. In Electrode Materials for Energy Storage and Conversion; CRC Press: Boca Raton, FL, USA; Taylor & Francis Group: London, UK, 2021; pp. 171–212.
  20. Arun, T.; Kavinkumar, T.; Udayabhaskar, R.; Kiruthiga, R.; Morel, M.J.; Aepuru, R.; Dineshbabu, N.; Ravichandran, K.; Akbari-Fakhrabadi, A.; Mangalaraja, R.V. NiFe2O4 Nanospheres with Size-Tunable Magnetic and Electrochemical Properties for Superior Supercapacitor Electrode Performance. Electrochim. Acta 2021, 399, 139346.
  21. Kumar, S.; Kumar, P.; Singh, N.; Kansal, M.K.; Kumar, A.; Verma, V. Highly Efficient and Sustainable MXene Based Heterostructure Composites Filled with Ferrites and MWCNTs to Mitigate the Radiation Interference in X-Band Frequency Region. Mater. Sci. Eng. B 2022, 282, 115798.
  22. Ayman, I.; Rasheed, A.; Ajmal, S.; Rehman, A.; Ali, A.; Shakir, I.; Warsi, M.F. CoFe2O4Nanoparticle-Decorated 2D MXene: A Novel Hybrid Material for Supercapacitor Applications. Energy Fuels 2020, 34, 7622–7630.
  23. Arun, T.; Dhanabalan, S.S.; Udayabhaskar, R.; Ravichandran, K.; Akbari-Fakhrabadi, A.; Morel, M.J.; Arun, T.; Dhanabalan, S.S.; Akbari-Fakhrabadi, A.; Morel, M.J. Magnetic Nanomaterials for Energy Storage Applications; Springer: Cham, Switzerland, 2022; pp. 131–150.
  24. Guo, Z.; Ren, P.; Lu, Z.; Hui, K.; Yang, J.; Zhang, Z.; Chen, Z.; Jin, Y.; Ren, F. Multifunctional /Cellulose Nanofiber Composite Films with Asymmetric Layered Architecture for High-Efficiency Electromagnetic Interference Shielding and Remarkable Thermal Management Capability. ACS Appl. Mater. Interfaces 2022, 14, 41468–41480.
  25. Yang, X.; Liu, Y.; Hu, S.; Yu, F.; He, Z.; Zeng, G.; Feng, Z.; Sengupta, A. Construction of Fe3O4@MXene Composite Nanofiltration Membrane for Heavy Metal Ions Removal from Wastewater. Polym. Adv. Technol. 2021, 32, 1000–1010.
  26. Xu, J.; Zeng, G.; Lin, Q.; Gu, Y.; Wang, X.; Feng, Z.; Sengupta, A. Application of 3D Magnetic Nanocomposites: MXene-Supported Fe3O4@CS Nanospheres for Highly Efficient Adsorption and Separation of Dyes. Sci. Total Environ. 2022, 822, 153544.
  27. Zhang, Z.; Wang, B.; Han, R.; Jin, F.; Zhang, N.; Zhang, T.; Wang, D. 3D 3O4 as Cathode Additive for Rechargeable Lithium−Sulfur Batteries. Adv. Energy Sustain. Res. 2022, 3, 2100167.
  28. Thirumurugan, A.; Akbari-Fakhrabadi, A.; Joseyphus, R.J. Surface Modification of Highly Magnetic Nanoparticles for Water Treatment to Remove Radioactive Toxins. In Green Methods for Wastewater Treatment; Springer: Cham, Switzerland, 2020; pp. 31–54.
  29. Arun, T.; Mohanty, A.; Rosenkranz, A.; Wang, B.; Yu, J.; Morel, M.J.; Udayabhaskar, R.; Hevia, S.A.; Akbari-Fakhrabadi, A.; Mangalaraja, R.V.; et al. Role of Electrolytes on the Electrochemical Characteristics of Fe3O4/MXene/RGO Composites for Supercapacitor Applications. Electrochim. Acta 2021, 367, 137473.
More
Academic Video Service