Merits and demerits of various fabrication techniques of MSCs.
With the boom in the development of micro-electronics for wearable and flexible electronics, there is a growing demand for micro-batteries and micro-supercapacitors (MSCs). Micro-supercapacitors have garnered a considerable attention for the evolution of these energy storage micro-systems. The choice of electrode material plays a pivotal role in the fabrication and development of MSCs. Recently, a new emerging family of two-dimensional transition metal (M) carbides or nitrides (X) cited as 2D MXene has emerged as a novel material. Due to its exceptionally high electronic conductivity ̴10,000 S cm−1, high charge storage capacity and easy processing capability helps to use MXene as the promising candidate for micro-supercapacitors electrodes. Taking the advantage of such exceptional properties. MXenes have been explored enormously in stacked as well as in interdigital architecture for on-chip micro-supercapacitors (MSCs). This book chapter includes a recent advancement of MXene based MSCs, with a brief overview of synthesis and fabrication techniques.
- 2D MXene
- Wearable and flexible electronics
- Energy storage
There is an increase in demand for flexible and solid-state on chip micro-electronics for smart wearable micro-devices for energy, environmental, biological, medical and various other applications which can be either wireless or integrated with solar or piezoelectric energy harvesters. Great efforts have been made by the scientists to design and develop smart as well as portable microsystems, primarily for self-powered and on-chip integrated power systems. To cope with the increasing demand of micro-electronics, there is an abrupt rise in the demand of micro-energy storage devices. However, micro-batteries are restricted due to their limited life and power density. Micro-supercapacitors (MSCs) hold the best alternate to the micro-batteries, despite the lower energy density. In contrast, MSCs can demonstrate superior cycle life, faster charge/discharge rates, high power density as well as overall stable performance which is promising . Presently, MSCs have two types of architecture, one with the conventional sandwich type and others are in-plane interdigital pattern type as shown in Figure 1(a,b), . Generally, the interdigitated coplanar design offers better performance due to the short ion diffusion distance which gives the enormous surface area. Thus, exhibiting an excellent rate capability, high-power density and ease of integration with micro-devices [1, 4, 5].
Two-dimensional (2D) materials like graphene, h-BN, Transition metal dichalcogenides (TMDCs), black phosphorus (BP), MXenes and 2D metal oxides and hydroxides etc. are most widely used in energy storage applications due to their outstanding electronic, mechanical, optical and physio-chemical properties . Carbon based materials including Carbon , carbide derived carbon , onion-like carbon , graphene , Carbon nano tubes (CNT) , laser scribed graphene  displays high electronic conductivity and relatively large surface area but due to electric double layer formation, they lack high energy density. Similarly, pseudocapacitive materials such as transition metal oxides like MnO2 , MoO3 , conductive polymers  as well as TMDs  which suffer from low electronic conductivity with reasonable power and cycling performance has been already explored in Micro-supercapacitor devices applications. But, MXenes have garnered great attention from the scientific community all over the world since their discovery in 2011, by Naguib and group . A large family of two-dimensional early carbides, nitrides and carbon nitrides produced by selective etching of A layer (typically Al and Ga) from the precursor layered ternary carbides/nitrides (MAX phases). Their general formula is Mn + 1XnTX (n = 1, 2, 3), where M represents a Transition metal, X is carbon and/or nitrogen, T stands for surface termination groups (-F, -OH, -O etc.) . In particular, the dual nature of MXenes that is superior ion transport due to inner transition metal carbide layer as well as property to exhibit fast redox reaction because of large active sites [18, 19]. MXenes combine high electronic conductivity of MAX phases as well as hydrophilic nature due to the surface terminations such properties make them a considerable candidate for a host of applications. Ti3C2TX is one of the most studied member of MXene family, exhibiting a high electronic conductivity up to ̴ 2.4 × 104 S/cm and volumetric capacitance 1500 F/cm3 with good rate capability of 10 V/s in acidic electrolyte . Hence there is plenty of room to design and develop MXene based Micro-supercapacitor devices . The 2D nature, excellent mechanical stability and exceptionally tunable physio-chemical properties makes MXenes, the best candidate for MSC device. This book chapter includes various direct–indirect techniques to fabricate MXene based MSC device.
2. MXenes: brief review
There are generally two methods to synthesize MXene i.e., (1) top-down approach which includes selective etching or exfoliation of metal layer and (2) bottom-up approach including chemical vapor deposition (CVD), template assisted growth method. Wet chemical etching i.e., fluoride based acids are most commonly reported methods to etch “A” element, generally group IIIA and IVA group (Al or Si) elements from MAX phases (one or several atomic layers) which are replaced by functional groups, where M is termed as early transition metals, from group IIIB to IVB, and X is carbide/nitride by using different wt % of fluoride containing acid such as HF or mixture of LiF-HCl acid [17, 20, 21]. The first ever report to synthesis MXene by eliminating the aluminium layer from Ti3AlC2 (MAX) by using hydrogen fluoride (HF) in the range of 10 to 50 % concentration of etchant . The exfoliated 2D Ti3C2Tx possess excellent 2D sheets like morphology almost similar to graphene sheets as shown in Figure 1(c,d) . To avoid highly acidic HF acid, various other methods have been developed to produce in-situ HF salts comparatively less hazardous than HF. Recently, a new approach to etch with molten salts allows to dissolve A-element at high temperature . This method demonstrated the complete removal of Fluorine ions and found to be much purer MXene than one etched with only HF. The presence of surface functional groups like -OH, -F and -O etc. improves the hydrophilic character of MXenes which further enhances the stability. The reaction mechanism of firstly synthesized Ti3C2TX (MXene) by etching Al layers from Ti3AlC2 (MAX phase) with HF is given in Figure 2(a) .
Reaction (2) and (3) gives rise to the surface terminations like -O, -OH, -F etc., respectively [17, 24]. MXenes have three possible structures with different layers of stacking as shown in Figure 2(b), . The tentative elements of MXene precursor in the periodic table predicted till now presented in Figure 2(c) .
The timeline of synthesis of MXene in different year is given in Figure 3(a).  Choice of synthesis and processing method including precursors etchant, intercalant, reaction sonication time etc. strongly influence the properties of resultant MXene. Mild alkali etchants like NaOH  and NaBF4  were also proposed to synthesis Ti3C2 by high temperature hydrothermal etching of Al layer from Ti3AlC2. This method extended to other MXenes such as Nb2C . Similarly, molten ZnCl2 were used for different MAX phases like Ti3AlC2, Ti2ZnN, Ti2AlC and V2AlC to substitute Zn2+ ions . Another report suggested a fluoride free-electrochemical etching at room temperature synthesis of Ti2C and Ti3C2 in dilute HCl  and NH4Cl/TMAOH . Also, a naturally delaminated MXenes with better electronic conductivity can be produced using minimally intensive layer delamination (MILD) without the use of further handshaking or sonication of MXenes . More than 20 different types of MXenes have been synthesized experimentally . Figure 3(b) represents the different etching methods that are used to synthesis different MXene products .
2.2.1 Electrical conductivity
MXenes have been extensively investigated by computational methods [31, 32], MXenes can be categorized into three types i.e., metallic, semi-metallic and semi-conducting . Generally, bare MXenes have very high electronic conductivity with high density of states (DOS) at the fermi level. Electronic properties of MXenes are strongly influenced by the surface, morphology and stacking behavior of MXene sheets. Delaminated MXenes flakes show ultra-high electronic conductivity of upto 9880 Scm−1, which can be further tuned by modifying the surface-terminations . In addition to this, MXenes strongly depends on synthesis procedure which can be achieved by varying the synthesis conditions. HF etched highly defective MXene exhibits electronic conductivity of 1,000 Scm−1. Whereas it improved to 4600 Scm−1 for powder and further enhanced to 6500 Scm−1 for delaminated MXene thick films by simply varying the etching and sonication conditions . Although, Theoretical investigations shows the high electronic conductivity in MXenes. But there is still lack of knowledge and experimental expeditions to synthesize such exceptional MXene with control over surface chemistry.
2.2.2 Surface morphology
MXenes are synthesized by MAX precursors where M atoms are close packed and X atoms at interstitial sites . Generally, MXenes have hexagonal close-packed structure with different order of M atoms in which M2X follows ABABAB type order with hexagonal-stacked packing while M3X2 and M4X3 follows ABCABC type order with face-centered cubic stacking . A study published by wang et al., Surface moieties play a key role in altering the properties of MXenes. The orientation and interaction between the terminal groups like -OH, -O, -F etc. strongly enhances interlayer hydrogen bonds which further improves the quality of MXenes. . Also, the hydrogen bonding in MXene is highly influenced by surface terminations and interlayer spacing. Depending upon the occupancy of a functional group like -OH, -F and -O etc. the properties can be tuned for the respective application. Intercalating the MXenes with ions, further gives a chance to mitigate the restacking behavior of MXene sheets for better performance, leading to display clay-like-behavior . There is a lot to study and prepare pure MXenes for future energy applications.
2.2.3 Mechanical properties
MXenes exhibit peculiar physical and chemical properties which directly contribute to their mechanical behavior such as young’s modulus, stiffness, defect generation, surface and elastic properties. Defect-rich MXenes with different terminal groups has strong covalent bonding with transition metal ion. Overall, there are various parameters which can be tunable to produce high performance MXenes. There are several theoretical studies on the mechanical, electronic as well as thermal properties of different types of MXenes [31, 39, 40, 41, 42, 43]. Experimentally the young’s modulus of Ti3C2O2 and Ti3CO2 was found to be 466 GPA and 983 GPA , these values were almost closer to the value predicted by theoretical simulations of 502 GPA . Theoretical studies claims that M2X exhibit much stronger in contrast to M3X2 and M4X3. But there is no experimental evidence to prove. However, in a study , A 5 μm thick paper film of Ti3C2Tx/PVA composite was able to hold ̴ 15,000 times its weight, which is evident to its strong wear and tear resistance property. Based on the surface terminations, there is a chance to modify surface properties of MXenes. Further investigations are needed to tune and enhance its nature.
3. Micro-fabrication techniques
Photolithography is a most promising technique at industrial scale which enables on-chip fabrication of high-resolution interdigital patterns of microelectrochemical systems (MEMS), Integrated Circuits (ICs), and complementary metal-oxide-semiconductors (CMOS) devices on various substrates with the help of computer-generated photomasks and photoresist designs. Recently, Jiang
3.2 Inkjet printing
Inkjet printing is a very popular technique for fabricating MSCs with excellent precision of designed pattern on various non conducting substrates. Nowadays, inkjet printing is gaining momentum in the scientific community. One can get desired thickness of printed layer to meet the certain applications. As name suggests inkjet printing is solely depends upon the prepared liquid ink.
There are three basic parameters which defines the behavior of the liquid inks:
1. Reynolds No. (Re)
2. Weber (We)
3. Ohnesorge (Oh)
Where ρ is the density (Kg/m3), η is the dynamic viscosity (N.S/m2), γ is the surface tension (N/m), v is the velocity (m/s), a is the nozzle diameter (m) . To generate, stable ink droplets, numerical simulations have demonstrated that the rheology behavior of the ink should be in the range of 1 < Z < 10 for better results. Also, to predict the rheological characteristics of a drop of ink, the inverse Ohnesorge number Z is used i.e., Z = 1/Oh. . As increase in demand of self-charged and wearable devices,highly functionalized conductiveTi3C2Tx (MXene) has attracted attention to directly prepare a highly stable conductive ink in various organic solvents. Inkjet printing is the cheapest and most viable technique to fabricate MXene based MSCs. Recently, Zhang et al. fabricated additive-free MXene ink based MSCs on flexible substrate shown in Figure 4(a), N-Methyl-2-pyrrolidone (NMP) based MXene ink shows excellent volumetric capacitance of 562 F/cm3 by inkjet printing. Demonstrating stable ink formulation in different organic solvents displayed in Figure 4(b). The extrusion printed patterns exhibits power density as high as 11.4 μWcm−2. Also, by adjusting the printing pass, the authors were able to reduce the sheet resistance upto 35 Ω/sq. from 445 Ω/sq. the areal capacitance and cycling stability of inkjet and extrusion printed MSC is given in Figure 4(c,d). This study opens a new technique to fabricate low cost MXene ink-based MSC devices . MXene aqueous ink with excellent oxidation resistance power were directly printed on paper substrate. The hybrid MXene suspension capped with sodium ascorbate (SA) displays the superior stability of upto 20 days. Due to its oxidation resistance nature and large interlayer spacing the conductivity of SA MXene improves to 119 Scm−1 this shows that there is still big room to develop MXene ink based printable devices for MSC Application .
3.3 Laser scribing
Laser engraving is another emerging cost-effective technique for the fabrication of MSCs on various customized substrates. Precise resolution with fast scanning speed makes this technique a superior approach in the field. But with all above benefits, there are few difficulties faced during the optimization of wavelength, resolution and accurate speed suitable for the fabrication of MSCs on different substrates. Tang and co-group demonstrated the direct laser writing of Ti3C2Tx interdigital electrodes by tuning the direction of laser scanning and rate. Interlayer spacing of restacked MXene was increased due to high photothermal oxidation effect of direct laser writing which enhanced the ion transport nature of the films . Wang et al., fabricated double sided flexible asymmetric MSCs on thin nickel sheet by using spray coating technique followed by cutting of interdigital patterns by UV laser. By increasing the mass of active material, the maximum capacitance improved to 34 mF cm−2 approximately double as compared to the previous one. The fabricated double-sided device displayed considerable energy density of 2.62 μWhcm−2 at 2 mA cm−2 . Further, Kurra and co-members reported a high areal capacitance based on clay-like MXene MSCs fabricated directly on paper by using a CO2 laser. Clay-like MXene shows superior power density of 46.6 mWcm−2 at energy density of 0.77 μWhcm−2, opening a new method to fabricate on-paper MSC devices .
3.4 Screen printing
Screen printing technology is one of the popular traditional technique to transfer predesigned ink patterns of active materials on various substrates. Important features of this technique are its scalability, reproducibility and repeatability. The screen printing technique is simple with high efficiency unlike other printing techniques, showing the enormous opportunity to explore. This inexpensive method can be used manually or even by automated machines. Generally, the setup includes the mesh screen with little gap between the substrate. With the help of squeegee, the ink is flooded over the screen mesh to print on the substrate . Screen printing gained considerable attention to directly print MXene ink-based electrodes directly on a target substrate. Screen printing solely depends on rheological properties of ink which should be highly viscos and show a good shear thinning behavior. Additionally, the size and resolution of electrodes depends on mesh size. Recently, screen printed MSCs were fabricated on paper by using homogeneous ink of MXene sediments. The perfectly tuned thickness of MSCs reduced the sheet resistance upto 2.2 Ω sq−1 and gives excellent electrical conductivity of upto 450 Scm−1. The energy density reached to 158 mFcm−2 which is highest of its kind . A two-step screen printing technique is employed to fabricate asymmetric MSC with interdigital pattern on paper as well as PET substrate. High energy density of 8.8μWhcm−2 in PVA-KOH was observed, far superior than many of other reports . There are advantages of the technique to get high mechanical stability on different substrates which definitely enhances the electronic conductivity of the fabricated devices.
3.5 3D printing
3D printing technology has attracted lot of attention for scalable fabrication of 3D architectures for the development of small and portable electronics. Recently a new trend has been introduced to fabricate 3D MSCs. This method is less complex and easy to handle compared to other lithography techniques. MXenes are the emerging material to be introduced by this technique for the fabrication of gel-type ink-based 3D MSC device to enhance its areal and volumetric capacitance. Recently, Orangi et al., fabricated an ultra-stable gel-type MXene ink based MSC given in Figure 5(a) by modifying its viscoelastic behavior in universal water solvent. The as fabricated device Figure 5(b) displays a maximum energy density of 51.7μWhcm−2. Further optimizations of active material layer have been done to further enhance the areal capacitance. Good adhesion & no change of electrochemical performance, even on applying stress and strain on the device given in Figure 5(c,f). The cyclic voltametric curves of all MSCFs and the best performing MSCF-10 as shown in Figure 5(d,e) . Similarly, Free standing Ti3C2Tx (MXene) ink-based 3D MSCs were fabricated followed by freeze drying for shape retention. To increase the stability and electrical conductivity, optimizing the mass loading to get the better viscoelastic behavior are the key parameters to obtain high areal capacitance. The maximum areal capacitance of 2.1 Fcm−2 at 1.7 mAcm−2 was achieved by a single MSC device. This unique technique has a wide base to explore micro-supercapacitor applications just by playing with the rheological properties of inks .
3.6 Other techniques
Unconventional methods have also been employed to fabricate the MXene based MSCs. A group reported the direct writing of highly concentrated MXene-in-water inks of upto 30 mg/mL in water on different substrates by using commercial roller ball pen. Interdigital electrodes were designed to fabricate Micro-supercapacitors. Areal capacitance of single MXene MSC was 5 mFcm−2 and by joining four MSC devices in series, the potential window reached upto 2.4 V which is evident for the development of flexible MSC devices . Zhang
|Photolithography||Direct||Wafer-scale manufacturing, uniform & high-resolution patterning [47, 48].||Multi-step process, template assisted, time consuming method .|
|Inkjet and Extrusion Printing||Indirect||Scalable production, customized design, less wastage of material [52, 62].||Uncontrollable procedure of ink synthesis, Low resolution, nozzle jamming is one of the main disadvantages of this technique .|
|Laser Scribing||Direct||Cost effective, fast simple, high controllability [54, 55].||Confined to very few types of materials .|
|Screen Printing||Indirect||Highly scalable and fast process .||Relatively low-resolution power|
|3D Printing||Indirect||Controllable design of patterns, versatile thickness control .||Limited to few materials, complex processibility .|
|Electrophoretic Deposition||Direct||Economically viable, facile procedure .||Limited applicability.|
|Vacuum-assisted-filtration||Indirect||Easy process, controlled thickness .||Low resolution, size and shape limited.|
4. MXene and its 2D hybrids for micro-supercapacitors
4.1 MXene based materials
In the past few years, MXenes have shown promising results for micro-supercapacitor applications. Due to their unique morphology, high metallic conductivity
4.2 MXene and carbon materials
Recently, Kim et al., reported a scalable production of MXene/CNT based MSCs with a 500 nm gap between the interdigital fingers exhibiting fast ion diffusion for superior conductivity. High areal capacitance of 317.3 mFcm−2 was achieved at 50 mVs−1 by composite of S-DWCNT/MXene in PVA-H2SO4 gel electrolyte. It is also observed that by decreasing the electrodes gap 10 μm to 500 nm, improves the ionic transfer rate, leading to increase in areal capacitance and energy density . A 3D MXene/rGO self-healable aerogel MSC were reported by Yue and group. The fabrication process is shown in Figure 7(a,b) They employed new approach to fabricate highly stable device by keeping in focus to real time applications. Fabricated device was encapsulated into self-healing Polyurethane (PU) which enabled the device to adhere the external damage. The composite aerogel exhibited an exceptional recovery of electronic and mechanical properties even after full breakdown and shows the areal capacitance of 34.6 mF cm−2 at 1 mVs−1, the areal capacitance and Cycling stability is shown in Figure 7(c,d) . Couly
In another report by chen and group, MXene-MoS2 based free standing MSCs were fabricated by simple and low-cost vacuum filtration method followed by carving of interdigital patterns with laser source. By introducing the MoS2 into MXenes which further enhances the electrochemical performance with almost 60% increase as compared to pristine MXene. i.e., the fabricated device displays a high specific capacitance of 173.6 F/cm3 at the scan rate of 1 mV/s, MSC shows around 98% of capacitance retention with 89% of coulombic efficiency even after 6000 cycles along with several bending angle of device upto 150 ̊. The above study demonstrated huge potential of TMDs which can be introduced with MXenes to make high performing MSC devices . Li
|Material||Method||Electrolyte||Potential Window||Device Performance||Specific Capacitance||Capacitance Retention||References|
|Energy Density||Power Density||Areal||Volumetric|
|Ti3C2Tx (100 nm-25 μm)||Photo-lithography||0 to 0.6||_______||PVA-H3PO4||0.5 mFcm−2 @120 Hz||30 Fcm−3 @120 Hz||_______|||
|Ti3C2Tx/CNT 500nm||FIB Lithography||PVA-H2SO4||0 to 0.6||_______||_______||317 mFcm−2 @ 50mVs−1||_______||_______|||
|Ti3C2Tx N = 25|
Ti3C2Tx N = 5
|PVA-H2SO4||0 to 0.5||_______|
|PVA-H2SO4||0 to 1||100.2 mWhcm−3|
|108.1 mF cm−2 @1 Ag−1|
48.4 mFcm−2 at 1Ag−1
|720.7 Fcm−3 @1 Ag−1|
|Ti3C2Tx||Laser Writing||3 M H2SO4||0 to 0.6||0.25 μWhcm−2||2.94 mWcm−2||15.03 mFcm−2||______||105% (10,000)|||
|Double sided Zn//MXene (Asymmetric)|
|PVA- Zn (CF3SO3)2|
|0 to 1.1|
0 to 0.8
52.3 mFcm−2 @2mAcm−2
|Clay like Ti3C2Tx||Laser Writing||PVA-H2SO4||0 to 0.6||0.77 μWhcm−2||46.6 mWcm−2||25 mFcm−2||______||92% (10,000)|||
|Ti3C2Tx Sediments||Screen Printing||PVA-H2SO4||0 to 0.6||1.32 μWhcm−2||778.33 μWcm−2||158 mFcm−2||______||95.8% (16,000)|||
|MXene//Co-Al layered double hydroxide|
|0.4 to 1.45|
0 to 0.6
|40.0 mF cm−2 @0.75bmAcm−2|
|Ti3C2Tx||3D Printing||PVA-H2SO4||0 to 0.6||8.4 μWhcm−2||3.7 mWcm−2||168.1 mFcm−2||______||______|||
|Ti3C2Tx||3D Printing||PVA-H2SO4||0 to 0.6||0.0244 mWhcm−2||0.64 mWcm−2 @ 4.3 mAcm−2||2.1 Fcm−2 @1.7 mAcm−2||______||90% (10,000)|||
|Ti3C2Tx||Direct Writing||PVA-H2SO4||0 to 0.6||______||______||5mFcm−2||______||______|||
|l-Ti3C2Tx||Stamping Strategy||PVA-H2SO4||0 to 0.6||0.63 μWhcm−2||0.33 mWcm−2||56.8 mFcm−2 @ 10mVs−1||______||93.7% (10,000)|||
|Ti3C2Tx||Laser jet Printing||PVA-H2SO4||0 to 0.6||6.1 mWhcm−3||______||27.29 mFcm−2 @0.25 mAcm−2||______||______|||
|Ti3C2Tx||Scratch method||PVA-H3PO4||0 to 0.7||2.3 mWhcm−3||159.6 mWcm−3||25.5 mFcm−2|
|PEDOT/Ti3C2TX 100nm||Spray Coating||PVA-H2SO4||0 to 0.6||______||______||2.4 mFcm−2 @ 10mVs−1||______||______|||
|Free-standing Ti3C2Tx – MoS2||Laser Engraving||Gelatin-ZnSO4||0 to 0.8||15.5 mWhcm−3||0.97 Wcm−3||_______||173.6 Fcm−3 @1mVs−1||98% (6,000)|||
|s-Ti3C2Tx||Spray coating + Laser engraving||PVA-H2SO4||0 to 0.6||11–18 mWhcm−3||0.7–15 W cm−3||27.3 mFcm−2|
|356.8 Fcm−3 @ 0.2 mAcm−2||100% (10,000)|||
|90 nm Ti3C2Tx thin film||Dip Coating + Automated Scalpel patterning||PVA-H3PO4||0 to 0.6||______||_______||_______||1500 Fcm−3||_______|||
|Ti3C2TX-MSC 10 μm||Laser Etched||PVA-H2SO4||0 to 0.6||______||_______||_______||308 Fcm−3 @5mVs−1||93% (10,000)|||
|Ti3C2TX||Mask-assisted vacuum filtration||PVA-H2SO4||0 to 0.6||10.3 to 29.6 mWhcm−3||18.6 to 3.1 Wcm−3||23.6 mFcm−2||591 Fcm−3||97.8% (2,000)|||
|Ti3C2TX // Ti3C2TX-MoO2-AMSCs (Asymmetric)||Vacuum filtration + Laser cutting||PVA- LiCl||0 to 1.2||9.7 mWhcm−3||0.198 Wcm−3||̴19 mFcm−2||63 Fcm−3|
|Ti3C2TX||Vacuum filtration + Laser cutting||PVA-H2SO4||0 to 0.7||43.5 mWhcm−2|
|73–340 mFcm−2||183–162 Fcm−3||82.5% (5,000)|||
|Ti3C2TX on paper||Spray coating + Laser coating||PVA-H2SO4||0 to 0.6||1.48 mWhcm−3||189.9 mWcm−3||23.4 mFcm−2 @0.05 mAcm−2||_______||92.4% (5,000)|||
|Ti3C2TX -Graphene aerogel||Laser cutting||PVA-H2SO4||0 to 0.6||______||______||34.6 mFcm−2 @ 1 mVs−1||______||91% (15,000)|||
|Ti3C2TX//rGO (Asymmetric)||Spray coating||PVA- H2SO4||0 to 1||8.6 mWhcm−3||0.2 Wcm−3||2.4 mFcm−2 @2 mVs−1||80 Fcm−3||97% (10,000) - Interdigital|||
|Ti3C2TX/CNT (YSC)||_______||PVA-LiCl||0 to 0.9||2.55mWhcm−3||45.9 mWcm−3||_______||22.7 Fcm−3 @ 0.1 Acm−3||99% (1,600)|||
|Ti3C2TX/rGO||_______||PVA-H3PO4||0 to 0.8||13.03 mWhcm−3||0.59 Wcm−3||_______||586.4 Fcm−3 @ 10 mVs−1||______|||
|RuO2/Ti3C2TX||Screen printing||PVA-KOH||0 to 0.6||13.5 mWcm−3||48.5 Wcm−3||_______||864.2 Fcm−3 @ 1mVs−1||90% (10,000)|||
|PANI/MXene//MXene||_______||1 M H2SO4||0 to 1.4||65.6 WhL−1||1687.3 WL−1||______||231.4 Fcm−3 @ 10mVs−1||87.5%|
|MXene/Bacterial Cellulose||Vacuum filtration + Laser cutting||PVA-H2SO4||0 to 0.6||0.0055 mWhcm−2||______||112.2 mFcm−2||______||______|||
|Polyester @MXene||Electrospinning of fibers||PVA-H2SO4||0 to 0.6||0.38–0.67 μWhcm−2||0.09–0.39 mWcm−2||7.99 mFcm−2 – 18.39 mFcm−2||̴ 4.5 Fcm−3 @5 mVs−1||98.2% (6,000)|||
|MXene/PEDOT-PSS||Fiber coating||Conductive binder PEDOT-PSS||0 to 0.5||______||______||131.7 mFcm−1 @0.2 mAcm−1||______||90% (10,000)|||
|rGO/MXene Hybrid||Wet-spinning||PVA-H2SO4||0 to 0.8||5.5 μWhcm−1||510.9 μWcm−1|
|23.2 Fcm−3||82% (10,000)|||
5. Future perspective and outlook
Since the discovery of MXenes in 2011 by Naguib et al.  MXenes have become a best choice for micro-electrodes to develop on-chip and self-charged MSC for wireless and wearable electronics applications. There is a significant increase in research on MXene based MSC due to its extraordinarily high electronic conductivity, good volumetric capacitance and excellent advancement in properties.
But, the development of MXene based MSC are still in early stage with necessity of optimization of electrode material, suitable electrolyte, substrates and many more. Right now, the focal point of researchers is on the enhancement of areal capacitance and power density of the fabricated MXene based MSC devices. However, there is an act of negligence over its property to self-discharged in open-circuit which needs to be resolved as soon as possible. One solution to this is to further integrate MSCs device with energy harvester like micro-piezoelectric or solar power cell component which will improve long term charge-storage property instead of self-discharging.
Also, the choice of electrolyte plays an important role to enhance the electrochemical performance of MSC device. Generally, polymer gel electrolyte. Particularly, PVA-H2SO4 is widely used ion exchange for MXene based electrodes for micro-devices. But due to low voltage window there is a call for an alternative which can help to increase the stability and voltage window. So that, there is an urgent requirement to study different electrolytes and polymers to achieve better performing MSC. In contrast to polymer matrix electrolyte, a new emerging class of quasi-solid electrolyte called as ionogel which is more mechanically and thermally stable than the regular gel electrolyte. All this demonstrates the possibility of ionogel to be a potential candidate for MSCs. To further expand potential window there is a requirement to make asymmetric devices which can further increase the voltage range above 3 V for real time applications.
Despite recent developments of Ti3C2Tix (MXene) based MSCs. There is still a big room to synthesis new MXene materials and explore their properties for the better understanding of charge storage mechanism which later can pave the way for future MSCs devices.
This work was financially supported by the Department of Science and Technology (DST)-SERB Early Career Research project (Grant No. ECR/2017/001850), DST-Nanomission (DST/NM/NT/2019/205(G), DST/TDT/SHRI-34/2018), Karnataka Science and Technology Promotion Society (KSTePS/VGST-RGS-F/2018-19/GRD NO. 829/315).
Conflict of interest
The authors declare no conflict of interest.
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