Recent Advances in Two-Dimensional ... - ACS Publications

Subscriber access provided by READING UNIV

Review

Recent Advances in Two-Dimensional Nanomaterials for Supercapacitor Electrode Applications Kowsik Sambath Kumar, Nitin Choudhary, Yeonwoong Jung, and Jayan Thomas ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.7b01169 • Publication Date (Web): 22 Jan 2018 Downloaded from http://pubs.acs.org on January 22, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Energy Letters is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

Recent Advances in Two-Dimensional Nanomaterials for Supercapacitor Electrode Applications Kowsik Sambath Kumar,†‡ Nitin Choudhary,† Yeonwoong Jung,†‡ϕ Jayan Thomas*†‡‼

†

NanoScience Technology Center, University of Central Florida, Orlando, Florida 32816, USA ‡

Department of Materials Science and Engineering, University of Central Florida, Orlando, Florida 32816, USA ϕ

Department of Electrical and Computer Engineering, University of Central Florida, Orlando, Florida 32816, USA ‼

CREOL, College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816, USA Email: [email protected] ABSTRACT: Supercapacitors represent a major technology to store energy for many applications including electronics, automobile, military, and space. Despite their high-power density, the energy density in supercapacitors is presently inferior to that of the state-of-theart Li-ion batteries owing to the limited electrochemical performance exhibited by the conventional electrode materials. The advent of two-dimensional (2D) nanomaterials has spurred enormous research interest as supercapacitor electrode materials due to their fascinating electrochemical and mechanical properties. This review discusses the cuttingedge research on some of the key 2D supercapacitor electrode materials including transition metal dichalcogenides (TMDs), transition metal oxides and hydroxides, MXenes, and phosphorene. Various synthetic approaches, novel electrode designs, and microstructure tuning of these 2D materials for achieving high energy and power densities are discussed.

ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

TOC

The world’s appetite for energy generation/storage from the renewable sources like solar, wind, and hydro is directly driven by an exhaustive use of depleting fossil fuels. Unfortunately, the intermittent nature of these renewable energy sources makes them incompetent for the ever-increasing demand for energy.1-2 The development of sustainable energy generation/storage systems and technologies is critical to reliably cater the commercial/residential energy requirements and to reduce the severe economic impacts of intermittent energy sources.3 Rechargeable Lithium-ion batteries (LIBs) have already cemented their position as dominant energy sources powering almost all forms of consumer electronics and electric vehicles (EVs).4-5 Albeit the advantage of being high energy density provider, LIBs have the limitations of poor cycle life, low power performance, and fire hazards.6 Supercapacitors, also known as ultracapacitors, are currently being considered as an alternative technology to LIBs since they are safer, pack ~10 times more power density, and last for several tens of thousands to millions of charge/discharge cycles.7-8 Supercapacitor technology has been improving at a fast pace and are highly reliable as evidenced by its use in the emergency exits of Airbus 380.2 One of the major drawbacks of supercapacitors is their intrinsically low energy density. The limitation is mainly attributed to the purely electrostatic storage of charges in electrodes driven by the electrical double layer (EDL) formation, which strictly requires high surface area and specific pore sizes.9-10 Another group of


Page 2 of 36

Page 3 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

electrochemical capacitors (ECs), broadly known as pseudocapacitors, utilize fast and reversible faradaic reactions on the electrode surface (or near-surface) for charge storage. Supercapacitors with pseudocapacitive materials can achieve significantly higher energy density compared to EDL capacitor as they have a variety of oxidation states for redox charge transfer reactions. However, a relatively low electrical conductivity and poor cycle stability due to slow ion transfer rate are limitations, hampering their widespread commercial realization.11-12 The aforementioned limitations of the traditional ECs drive significant research interests for the development of novel electrode materials exhibiting excellent electrochemical performances to achieve high energy-density. In recent years, twodimensional (2D) materials have drawn considerable attention as supercapacitor electrode materials. 2D materials are ultrathin layered crystals which show unusual physiochemical properties at single or few-atom thickness. 2D materials offer several key advantages for the next generation electrochemical devices; (i) atomically thin 2D nanosheets provide a larger surface area due to complete exposure of the surface atoms, (ii) the edge sites in 2D nanosheets are chemically more reactive than basal planes and the open van der Waals gaps enable the intercalation of electrolyte ions and (iii) the high mechanical strength and flexibility at atomic dimensions allow them to be used in the next generation wearable electronics. For example, graphene, a 2D sheet of carbon has remained a major source of scientific fascination for energy storage over the last decade.13 Beyond graphene, a large family of 2D materials have been emerging as viable electroactive components for nextgeneration energy storage devices while taking over the functions initially assigned to LIBs. 2D transition metal dichalcogenides (TMDs) are considered as the major post-graphene contenders, which display unique properties of large surface area and variable oxidation states (e.g. +2 to +6 in MoS2) making them viable for both EDL and faradaic charge storage



mechanisms.14-15 The most interesting attribute of 2D TMDs is their different polytype (1T and 2H phase) structures which show extraordinary electrochemical performance and high operational voltage windows.16 Transition Metal Oxides and Hydroxides (TMOs and TMHs), pseudocapacitive materials commonly used in bulk forms, have intrinsically low electronic conductivities limiting fast ion diffusions, which makes them incompetent for high rate performances. However, developing TMOs and TMHs in the form of 2D nanostructures as nanofilms, nanosheets, nanoflakes, nanoplatelets, nanopetals, nanobelts, etc. significantly alters their inherent properties compared to their bulk counterparts. These nanostructures often provide high conductivity, easy ion diffusion and improved mechanical integrity.17-20 It should be noted that 2D TMOs and TMHs are not layered materials like graphene and 2D TMDs, but a similar "2D" terminology is used because of their ultra-small (a few atom) thickness, exhibiting extraordinary properties different from their bulk counterparts. 2D carbides and nitrides of transition metals i.e. MXenes have recently emerged as potential candidates for supercapacitor electrodes due to their large surface-to-volume ratio, high intrinsic conductivity, and abundant electrochemically active sites, leading to significant intercalation or pseudocapacitance through their transition metal chemistry.21 Phosphorene, an analog of graphene is emerging as a new 2D material, possessing puckered lamellae structure with weakly bonded layers of phosphorous atoms.22 Despite its high electrical conductivity, thermodynamic stability and fast ion diffusivity, phosphorene still remains largely unexplored as supercapacitor electrode material compared to other similar 2D materials. Hence, an array of novel electrode materials exhibiting EDLC or pseudocapacitive charge storage mechanism are currently being developed for high performance supercapacitors. Beyond materials development, synthesis of hybrid electrode materials comprising of two or more electrochemically active 2D nanomaterials (EDLC or pseudocapacitive) in the form of composites, core/shell structures, and heterostructures have


Page 4 of 36

Page 5 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

been simultaneously pursued.23-25 These hybrid designs introduce more electrochemical active sites, improved rate capability, and enhanced cycle stability in the supercapacitors owing to the synergistic effects enabled by high quality heterointerfaces, tunable electronic/chemical properties, and high structural stabilities. Nevertheless, the construction of novel supercapacitor device configuration using these electrodes is gaining significant attention as the energy density of the devices not only rely on the capacitive performance of the electrode, but also on the higher operational voltage window (i.e. Energy density = 1/2CV2, where C is the capacitance, V is operation voltage).8 For example, asymmetric supercapacitor device configuration utilizing two dissimilar electrodes having dissimilar voltage windows has enabled a significant boost in the energy density of supercapacitors in the past few years.26-27 This review emphasizes the recent developments of novel 2D electrode materials such as TMDs, TMOs and TMHs, MXenes, and Phosphorene and their electrochemical performances for developing high energy density supercapacitor electrodes and devices. The impact of crystal structures, crystalline phases, and electrical/chemical properties inherent to these materials on the supercapacitor electrode performances are discussed in detail. We also deliberate how the characteristic properties of these materials such as specific surface area, electrical conductivity, and porosity can be tuned by engineering their nanostructures into different form factors such as quantum dots, nanospheres, nanowires, and nanorods. Design principles for rationally integrating 2D materials with other electroactive materials to achieve hybrid electrodes (composites, core/shell, and 3D nanostructures) are also highlighted.

1. 2D Transition metal dichalcogenides (TMDs) electrodes. 2D TMDs are layered materials in which a unit cell is composed of a transition metal (M) layer sandwiched between two chalcogen (X) layers in the form of MX2 (where M: Mo, W and X: S, Se, or Te).28-29 The large surface area and variable oxidation states in TMDs allow electrical double-



layer and fast/reversible redox charge storage mechanisms. In addition, 2D TMDs exhibit high electrochemical activity derived from their edge sites, which offer large energy storage capability in supercapacitors.23, 30-32 Despite a plethora of research conducted on monolithic 2D TMDs based supercapacitor electrodes, their electrochemical performance is often limited by poor cycle life, inherently low electrical conductivity, large volume change during cycling, and restacking.33-34 For example, sheet-like morphology of MoS2 proposed by Soon et al32 provided large surface area for double layer storage; however, owing to its poor electrical conductivity, it exhibited a low specific capacitance of ~100 Fg-1 at a scan rate of 1 mVs-1. To circumvent these issues, 2D TMDs have been mixed, wrapped, or deposited with highly conductive/electroactive materials such as carbonaceous materials and conducting polymers (CPs) using various top-down/bottom-up synthetic techniques and their combinatorial approaches.35-42 Most notably, the development of metallic TMD nanomaterials, as discussed later in this section, are revolutionizing the supercapacitor research by offering exceptionally high electronic/ionic transport and unprecedented charge storage ability.16, 43-44

1.1. TMDs/Carbonaceous materials hybrids. Typically, carbonaceous materials like graphene, carbon nanotubes, carbon aerogel, etc. have high electrical conductivity and surface area. Developing TMD hybrids or composite materials with carbon-based materials provide synergistic effect of the two materials; carbon offering conductive channels and enhancing interfacial contact, while TMDs contribute short ion diffusion path and successive short electron transport path, thus enhancing overall electrochemical performance.45-46 A 3D nanocomposite of MoS2/MWCNT (multiwall carbon nanotube) prepared by a facile one-pot L-cysteine-assisted hydrothermal process offered a large surface area and fast ionic transport properties and delivered a high specific capacitance of 452.7 Fg-1 with 95.8% retention after 1000 cycles.47 Almost three times increase in capacitance (149.6 Fg-1 to 452.7 Fg-1) was


Page 6 of 36

Page 7 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

observed in the composite compared to bare MoS2. Another interesting electrode was designed by incorporating 2D MoS2 and reduced graphene oxide (rGO) nanosheets into aligned MWCNT fibres.48 Figure 1a-c are the Scanning Electron Microscopy (SEM) images of the aligned MWCNT fibres and its hybrids with MoS2 and rGO. The solid-state supercapacitor fabricated using MoS2-rGO/MWCNT fibre electrode operates at a stable potential window of 1.4 V as shown by the CV curves in Figure 1d. Moreover, the device yields 100% coulombic efficiency in bending state even after 7000 cycles (Figure 1e). A high energy density of 78.9 Whkg-1 and an operational voltage window of 2.0V have been reported in asymmetric supercapacitor (ASC) based on flower-like MoS2 grown on graphene



nanosheets (GNS) and MnO2/Graphene hybrid electrodes.49 This is an impressive achievement since the energy density of supercapacitor is approaching closer to thin film LIBs (~ 100 Whkg-1).5 1.2. TMDs/conductive polymers (CPs) hybrids. Conducting polymers (CPs) are another promising additives which significantly enhance the capacitive performance of 2D TMDs owing to their high redox active capacitance, moderately high electrical conductivity,

Figure 1. Different hybrid designs for high-performance TMDs supercapacitors. SEM images of (a) aligned MWCNT sheet (b) MWCNT/MoS2 hybrids, and (c) tightly knotted MoS2/MWCNT and rGO/MWCNT fibers. (d) CV curves of rGO/MWCNT (cathode) and MoS2-rGO/MWCNT (anode) in different voltage windows. (e) Cycle test of the fiber-based asymmetric device at a current density of 0.55 Acm-3. Adapted with permission from ref 48, Copyright 2015 Wiley Online Library; (f) SEM and TEM images showing the formation of PANI nanoneedles on MoS2 nanosheets. (g) Ragone plot showing and energy and power density at different voltage windows (h) schematic representation of facile H+ ion intercalation into MoS2/PANI composite, Adapted with permission from ref 24, Copyright 2011 Wiley Online Library.

low cost, and high intrinsic flexibility.50-51 In-situ polymerization methods have been mainly employed to synthesize TMDs/CPs hybrids as this method yields a better dispersion of TMD


Page 8 of 36

Page 9 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

flakes in CPs while inhibiting restacking of TMDs layers.52 A controlled growth of polyaniline (PANI) nanowires on internal and external faces of the 3D tubular MoS2 have been reported via oxidative polymerization of aniline monomers. The hybrid electrode exhibited a faradaic behavior with a high specific capacitance of 552 Fg-1 at a current density of 0.5 Ag-1. The improved electrochemical performance was attributed to the unique 3D tubular design which facilitates access of electrolyte ions to the active sites of electrode surface.53-54 Following a similar approach, the morphological tuning of 2D MoS2 nanosheets has been achieved24 in which 1D PANI nanoneedle arrays vertically stand on either side of the exfoliated 2D MoS2 nanosheets, as shown in SEM and Transmission Electron Microscopy (TEM) images in Figure 1f. This highly electrochemically active 2D MoS2@PANI composite with large surface area and good electrical conductivity yield a high specific capacitance of 853 Fg-1 at a current density of 1 Ag-1. A very impressive energy density of 106 WhKg-1 (Figure 1g, h) was also achieved. 1.3. Metallic TMDs. Thus far, supercapacitors based on TMDs have mainly relied on the thermodynamically stable 2H phase which shows semiconducting yet poorly conducting characteristics. Recently, the introduction of metallic 1T phase in 2D TMDs is revolutionizing their potential for device applications. The high electrical conductivity and excellent ion intercalation capability in 1T TMDs facilitate electron/ion diffusion and dramatically enhance the specific capacity.44 Chhowalla research group16 demonstrated ~107 times higher electrical conductivity in 1T MoS2 films as compared to their semiconducting (2H-MoS2) counterparts. The electrode assembled by stacking exfoliated 1T- 2D MoS2 nanosheets, as shown in the SEM image of Figure 2(a) yields a high capacitance in the range of ∼400-700 Fcm-3 (Figure 2b) in various aqueous/organic electrolytes. This electrode can operate at 3.5 V in organic electrolytes and provides a coulombic efficiency of ~95% over 5,000 charge/discharge cycles (Figure 2c). 2D vanadium disulfide (VS2), an emerging



metallic TMD have been reported to form in-plane supercapacitors.43 Figure 2d is an SEM image of the ammonia assisted VS2 flakes in bulk VS2 precursor, where the thickness of

Figure 2 (a) SEM side view of the stacked 1T-MoS2 layers (b) Volumetric capacitance of the 1T MoS2 electrode at different scan rates and in different electrolytes. (c) Cyclic stability test of 1T MoS2 in different electrolytes. Adapted with permission from ref 16, Copyright 2015, Nature Publishing Group. (d) SEM image of the VS2.3NH3 precursor with inset showing a flake thickness of about 110 nm. (e) HR-TEM image of the exfoliated VS2 nanosheets along (001) facets. (f) Specific capacitance and coulombic efficiency of the metallic VS2 electrode Adapted with permission from ref 43, Copyright 2011 American Chemical Society.

individual flake is ~110 nm (inset of Figure 2d). The 2D VS2 nanosheets extracted from these ammoniated VS2 flakes were 4-5 atomic layers thick as shown in Figure 2e. Electrochemical characterizations revealed a specific capacitance of 4760 µFcm-2 without any capacitance loss even after 1000 charge/discharge cycles (Figure 2f).

2. 2D Transition Metal Oxides and Hydroxides Electrodes. 2D oxides and hydroxides of transition metals are promising supercapacitor electrode materials for their high chemical stability/compatibility, high specific capacitance, and environmental friendliness. In contrast to the bulk TMOs and TMHs, which show poor rate performances due to intrinsically low electronic conductivity impeding their fast ion diffusivity; their 2D counterparts provide an alternate route for compensating the aforementioned shortcomings by offering short diffusion


Page 10 of 36

Page 11 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

paths, high electronic conductivity, and large surface areas. In the following sections, we describe the development of 2D TMOs and TMHs based supercapacitor electrode materials. 2.1. 2D Transition Metal Oxides (TMOs). 2D TMOs (e.g., MnO2, Fe3O4, Co3O4, NiO, etc.) offer exciting properties as promising supercapacitor electrode materials not only because of their intrinsically rich redox activity, but also due to enlarged surface areas endowing surface sites for EDL charge storage.

55-62

Moreover, the thin/flexible TMOs

electrodes with high mechanical and chemical stabilities provide opportunity to integrate them with next-generation flexible devices.63-66 Among various TMOs, manganese dioxide (MnO2) have been extensively investigated owing to its low cost, non-toxicity, and high theoretical capacity (1370 Fg-1).56, 67-68 Ultrathin MnO2 nanosheets (MSs) (thickness ~2 nm) synthesized using a soft template method exhibited a specific capacitance of 774 Fg-1 at a current density of 0.1 Ag-1 (Figure 3a).18 The ASCs fabricated using MSsand graphene electrodes (GA) exhibited a very high energy density of 97.2 WhKg-1 with 97% capacitance retention after 10000 cycles. These electrodes could be designed into various pictures and patterns via screen printing (e.g., a panda design in Figure 3b), and were made flexible (Figure 3c). In a recent attempt,69 defects/vacancies were created in birnessite MnO2 (i.e. δMnO2, a 2D MnO2 allotrope with excellent capacitive properties) in a controlled manner to achieve additional cation intercalation sites. The exfoliated and reassembled δ-MnO2 nanosheets form 3D macroporous electrodes which provided a pseudocapacitance of ≥ 300 Fg-1 attributed to the synergistic effects between the defect content and Mn redox, which worked together to lower the charge transfer resistance and promote the ion intercalation.



Figure 3 (a) Specific capacitance vs scan rate, insert is capacitance versus discharging current density. Photographs of the (b) ‘‘panda’’ asymmetric MS/GA supercapacitor lighting up a red light emitting diode. (c) Electrodes demonstrating mechanical flexibility. Adapted with permission from ref 18, Copyright 2013 Springer Nature Publishing Group. (d) SEM image of Co3 O4 nanoarrays. (e) Specific capacitance vs charge and discharge current density. Adapted with permission from ref 76, Copyright 2013 Springer Nature Publishing Group.

Despite some successful demonstrations, 2D MnO2-only electrodes suffer from intrinsically poor electronic conductivities, resulting in low power density and rate performance. Thereby, MnO2 hybrids with conductive yet capacitive materials such as graphene, carbon nanotubes (CNTs) have been proposed.70-73 For example, a planar supercapacitor developed by using 2D δ-MnO2/Graphene hybrid exhibits a high rate capability ~208 Fg-1 at 10 Ag-1 and capacitance retention of about 92% after 7000 charge/discharge cycles.63 Iron oxide (Fe3O4) has also been used as an active 2D TMO component with carbon and graphene nanosheets to form hybrid composites.74-75 A 2D sandwich-like graphene supported Fe3O4 electrode formed by electrochemical method exhibited a capacitance of 329 Fg-1 at 0.5 Ag-1 and an excellent energy density of 85 WhKg-1 at power density of 2.4 kWKg-1.75 Uniformly distributed Fe3O4 on graphene sheets prevents aggregation of Fe3O4 nanoparticles offering a cycle life of 1000 cycles with 95% capacitance ACS Paragon Plus Environment

Page 12 of 36

Page 13 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

retention. Ultrathin Co3O4 is another potential pseudocapacitive electrode material offering low environmental impact, low cost, and great redox activity. A uniform nanosheets array composed of ~5 µm long, ~10 nm thick Co3O4 nanosheets (Figure 3d) developed by a twostep hydrothermal reaction exhibited a specific capacitance of 1782 Fg-1 at a current density of 1.8 Ag-1 (Figure 3e), and retained > 90% of initial capacitance after 2000 cycles.76 Porous 2D TMOs-based nanostructures play critical role in boosting its surface area, offering short pathways for charge transport, better contact with electrolyte, and accommodate substantial volume expansion during cycling processes.77 A novel 3D porous Co3O4 nanosheets structure exhibited a remarkable specific capacitance of 1500 Fg-1 at 1 Ag-1 and provided a high energy density of 15.4 WhKg-1 in asymmetric device configuration.78 In another report, a binder-free synthesis of mesoporous Co3O4 nanosheets arrays on the Ni foam using a two-step strategy of Co(OH)2 electrodeposition followed by calcination witnessed a high specific capacitance of 2735 Fg-1 at a current density of 2 Ag-1 in 2M KOH.79 Besides Co3O4, porous hollow spheres enabled by randomly oriented 2D Nickel Oxide (NiO) nanosheets electrode achieved a high specific capacitance of 600 Fg−1 at 10 Ag−1 and an excellent energy density of 19.44 Whkg−1.80 The good electrochemical performance in these electrodes is attributed to the enhanced ionic transport of electrolyte ions in the porous NiO nanosheets network. 2.2. 2D Transition Metal Hydroxides (TMHs) Similar to TMOs, transition metal hydroxides (TMHs) have been widely employed as high performance pseudocapacitive electrode materials in supercapacitors.81-85 However, their electrochemical performance is mainly dictated by their morphology and in bulk electrode structures, the shortcoming was found to be due to the inefficient utilization of active materials.27, 86-87

Specifically, scaling of bulk TMHs to their 2D counterparts enables facile ion/electron

transport, large strain accommodation during cycling, and reduced ion-diffusion barrier due to structural changes, which provides an excellent charge storage as well as high rate



capability.

20, 88-89

TMHs of Co (i.e. Co(OH)2) and Ni (i.e. (Ni(OH)2) have been mainly

explored in their 2D nanostructures. For example, a solid-state ASC consists of single layers of β-Co(OH)2 (Figure 4a) as cathode and N-doped graphene as anode delivered a high operation voltage of 1.8 V and an exceptionally high energy/power density of 98.9 Whkg1

/17981 Wkg-190. Moreover, the device retained 93.2% capacitance after 10,000 cycles. The

performance akin to LIBs is attributed to the 100% exposure of surface hydrogen atoms by five-atom thick Co(OH)2 single-layers to serve as electroactive sites for significant faradaic redox reactions as demonstrated in the schematic of Figure 4b. 2D Ni(OH)2 is another costeffective material that present excellent electrochemical properties for high energy density supercapacitors. Ultrathin, free-standing 2D nanosheets (thickness < 2nm) of ߙ -Ni(OH)2 were prepared using a microwave-assisted liquid-phase growth method.20 Figure 4c, d show the growth process and SEM image of the as-synthesized ߙ-Ni(OH)2 nanosheets. These ultrathin 2D nanostructures exposed majority of the atoms for surface-dependent electrochemical reaction processes, exhibiting a maximum specific capacitance 4172.5 Fg−1 at a current density of 1 Ag−1. Even at a higher rate of 16 Ag−1, the specific capacitance was maintained at 2680 Fg−1 with 98.5% retention after 2000 cycles (Figure 4e).


Page 14 of 36

Page 15 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

Figure 4 (a)TEM image of single-layer β-Co(OH)2 and colloidal ethanol dispersion displaying the Tyndall effect (b) Schematic illustration of the hydrogen adsorption/desorption process in the single-layer β-Co(OH)2 electrode. Adapted with permission from ref 90, Copyright 2014 Wiley Online Library. (c) Schematic illustrating synthesis of ࢻ-Ni(OH)2 nanosheets. (d) FESEM image of ࢻ-Ni(OH)2 nanosheets. (e) Specific capacitance as a function of current densities. Adapted with permission from ref 20, Copyright 2014 Nature Publishing Group.

Despite remarkable capacitive performance exhibited by single component 2D TMHs like Co(OH)2 and Ni(OH)2, these may suffer significant capacitance decay after prolong cycling at high current densities. To circumvent this issue, hybrids of 2D TMHs are being developed by growing/mixing them with highly conductive materials, metal oxides or with other 2D TMHs. For instance, single-crystalline Ni(OH)2 nanoplates were grown on 3D graphene sheets network.91 The composite delivered a high specific and rate capacitances of ∼1335 Fg-1 at 2.8 Ag-1 and ∼953 Fg-1 at 45.7 Ag-1, respectively. The energy density was estimated to be ∼37 Whkg-1 at a power density of ∼10 kWkg-1. 2D TMH/TMH hybrid electrodes present advanced supercapacitors due to their enhanced redox activity bestowed by multiple redox reactions in each participating TMH. 2D porous Ni(OH)2-Co(OH)2 hybrids were facilely prepared in ethylene glycol-water solution.92 These electrodes exhibit an excellent specific capacitance of 1537 Fg−1 at 0.5 Ag−1 and retained ~1181 Fg−1 even at a high current density of 10 Ag−1. The ASCs fabricated with carbonaceous electrodes achieved a high energy density of 33.7 Whkg−1 at a power density of 551 Wkg−1, and an operating voltage of 1.5V. Moreover, an excellent



cycling stability with 109% capacitance retention after 10000 cycles was observed. A novel Ni(OH)2/Co(OH)2 nanosheets architecture composed of electrodeposited Ni(OH)2 and Co(OH)2 consecutive layers was recently developed.93 These electrodes showed a specific capacity of 762 Cg−1 at the specific current of 1 Ag-1. An ASC using Ni(OH)2/Co(OH)2 as positive electrode and carbon nanofoam paper as negative electrode yielded a specific energy density of 101.3 Whg−1. TMHs-TMOs hybrids have also been explored to achieve high energy densities in supercapacitors. A hydrothermally grown ultrathin Ni(OH)2-MnO2 hybrid nanosheets array on 3D macroporous nickel foam exhibits an ultrahigh specific capacitance of 2628 Fg-1.94 The highly hydrophilic and ultrathin nature of hybrid nanosheets with high synergetic effects between Ni(OH)2 and MnO2 were responsible for the outstanding electrochemical performance. Nevertheless, the ASCs assembled using Ni(OH)2-MnO2 cathode and rGO as the anode provided a very high energy density of 186 Whkg-1 and a power density of 778 Wkg-1. 3. MXene Electrodes. The major limitation of low electrical conductivity in TMOs/TMHs needs modification of their structural morphology or developing their composites with highly conductive additives to effectively use them as supercapacitor electrodes. However, a material with inherently high electrical conductivity on its own holds great promise as an excellent energy storage electrode. MXenes, an emerging class of 2D supercapacitor electrode material possesses a high intrinsic electronic conductivity, good hydrophilic nature, and excellent mechanical stability.95-96 MXenes are a few atom thick transition metal carbides, nitrides or carbonitrides derived from MAX phase having a chemical composition of Mn+1AXn, where n = 1, 2, or 3, M is an early transition metal, A is mostly groups 13 and 14 element of the periodic table, and X is C and/or N.97 MXenes, developed by extracting A from MAX phase is denoted as Mn+1XnTx, where T represents surface termination groups (-O, -OH, and -F) left over from the etching process and x is the


Page 16 of 36

Page 17 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

number of terminating groups. Here, we describe several significant developments in the MXene-based supercapacitors. 3.1. Synthesis, Surface modification and Mass Loading. Gogotsi’s group at Drexel University pioneered the development of MXene-based supercapacitors.21, 98 They exfoliated Titanium Aluminum Carbide (Ti3AlC2) in the presence of hydrofluoric acid (HF) to produce 2D nanosheets of Titanium Carbide (Ti3C2) exhibiting graphene-like morphology with good chemical stability, electrical conductivity, and high ductility. A free-standing conductive paper made from these Ti3C2 MXene nanosheets exhibited a high volumetric capacitance of 340 Fcm-3 in KOH.98 Ghidiu et al. produced freestanding Ti3C2 with intercalated water adopting a much safer route using a solution of Lithium Fluoride (LiF) and Hydrochloric acid (HCl) as an etchant.99 The MXene produced was clay like paste that can be moulded to yield various shapes with high conductivity and can also be used as an ink to print MXene on various substrates. Electrochemical performance of these Ti3C2 freestanding films in 1M Na2SO4 exhibited a volumetric capacitance of 900 Fcm-3 at 20 mVs-1, gravimetric capacitance of 245 Fg-1 at 2 mVs-1 and magnificent cycle stability (100% capacitance retention after 10000 cycles). Outstanding performance of the LiF + HCl etched Ti3C2 compared to HF etched Ti3C2 is attributed to pre-intercalated water and smaller size of cation (H+) in electrolyte. Another approach to develop Ti3C2Tx films is simple dropping-mild baking method which demonstrated high gravimetric capacitances up to 499 Fg-1 even with low mass loading.100 To study the effect of surface chemistry on capacitive performance, Simon and coworkers101 modified Ti3C2Tx via (i) delamination of Ti3C2Tx by intercalation of Dimethyl Sulfoxide (d-Ti3C2) and (ii) chemical intercalation of K+ ion using potassium hydroxide (KOH-Ti3C2) and potassium acetate (KOAc-Ti3C2) (Figure 5a). Chemical intercalation of potassium salts replaced terminal fluorine with oxygen-containing functional groups leading



to 4-fold increase in capacitance. Delamination led to increase in surface area causing the dTi3C2 to exhibit outstanding volumetric capacitance of 520 Fcm-3 and a gravimetric capacitance of 325 Fg-1 at 2 mVs-1. This work led to a new approach of modifying surface chemistry of various MXenes to achieve better electrochemical performance. High mass loading of the active material is an important aspect when it comes to practical application of supercapacitors. Increase in material loading typically increases resistance and limits electrolyte accessibility leading to poor capacitive performance. Lin et al102 discovered that the Ti3C2 is exceptional since its layered microstructure helps in the electrochemical utilization of all the Ti3C2 sheets and exhibits high electronic conductivity. The electrode made from these nanosheets with the high mass loading of 7.6 mg achieved an areal capacitance of 579 mFcm-2 at 2 mVs-1 compared to 211 mFcm-2 with 1.8 mg material. Also, the good connectivity between Ti3C2 sheets makes the equivalent series resistance (ESR) value of high mass loading (0.90Ω - 7.6mg) Ti3C2 electrode material comparable to that of the low mass loading (0.83Ω - 1.8mg) material. This mass loading test opens up the significance of using 2D layered nanomaterials for achieving high energy for practical applications. 3.2. Flexible MXene. Developing flexible energy storage devices is highly necessary for designing next-generation smart electronics and wearables.103-105 Peng et al106 fabricated an all-Ti3C2Tx solid-state interdigital microsupercapacitor (MSC) by solution spray-coating of large size (3–6 mm laterally) HCl/LiF etched Ti3C2Tx as the current collector which is followed by spray-coating of small size HCl/LiF etched Ti3C2Tx (~ 1 mm) with more defects and edges on top as the electroactive layer. The device exhibited areal and volumetric capacitance of ~27 mFcm−2 and ~357 Fcm−3 respectively at scan rate of 20 mVs-1 with 100% capacitance retention after 10000 cycles at a scan rate of 50 mVs-1. Recently, a symmetric solid-state flexible fibre based MXene supercapacitor107 was developed using Ti3C2Tx flakes ACS Paragon Plus Environment

Page 18 of 36

Page 19 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

loaded on silver-plated nylon fibres as electrodes and PVA-H2SO4 hydrogel as the electrolyte. The fabricated fibre device exhibited a high areal capacitance of 328 mFcm−2 with excellent cyclability, flexibility, knittability and cycle stability. The capacitance remained at least above 80% under various deformation modes including bending, twisting, and knotting. At a scan rate of 2 mVs−1, it showed an energy density of 7.3 µWhcm−2 and a power density of 132 µWcm−2. These results promise a plethora of opportunities for powering wearable and flexible electronics applications employing MXenes and their heterostructures. 3.3. MXene Composites. Like other 2D materials, restacking and irreversible aggregation of 2D nanosheets is a potential problem in MXene electrodes as well, which essentially diminish the interlayer spacing and accessibility of ions for electrochemical utilization. Interlayer spacing can be modulated by developing MXenes composites by incorporating species like polymers,

108-109

carbon derivatives,

110-111

and metal oxides108, 112

into the layers. These interlayer spacers prevent restacking of the MXenes flakes and thus increasing electrochemical utilization of entire surface of the material. MAX phase-polymer composite was first developed by Ling et al. using poly (diallyldimethylammonium chloride) (PDDA) and PVA.113 Ti3C2Tx films on their own possess excellent mechanical and tensile strength (22 ± 2 MPa). Upon introducing PVA, Ti3C2Tx/PVA film exhibited four times increase in tensile strength. Introduction of PVA also prevented restacking and increased interlayer spacing of Ti3C2Tx flakes thus improving the accessibility of ions to deep trap sites. The composite showed maximum capacitance of 530 Fcm-3 at 2 mV/s. Zhao et al114 prepared sandwich-like MXene/CNT composite electrodes by alternate deposition of Ti3C2Tx flakes and CNT layers (Figure 5b). CNT provided faster diffusion paths and enlarged interlayer spacing between the Ti3C2Tx flakes for cation intercalation. A high volumetric capacitance of 350 Fcm-3 at 5 Ag-1 current density was achieved with no degradation even after 10000 cycles



for MXene/SWCNT papers (Figure 5c). Incorporation of rGO into Ti3C2Tx flakes increased the interlayer spacing and exhibited a volumetric capacitance of 435 Fcm-3 at 2 mVs-1.

Figure 5 (a) Schematic Illustration of the modifications of Ti3C2Tx: delamination and intercalation of K+ Adapted with permission from ref 101. Copyright 2014, Elsevier. (b) Cross-sectional SEM image of sandwich-like Ti3C2Tx/SWCNT (c) Cycling stability of sandwich-like Ti3C2Tx/SWCNT electrode at 5 Ag-1 Inset showing first 3 cycles of GCD. Adapted with permission from ref 114, Copyright 2014 Wiley Online Library.

Despite the high areal and volumetric capacitance, MXenes suffered from poor gravimetric capacitance because of their low surface area (30m2/g). Decorating MXenes with pseudocapacitive materials improves the surface area considerably. The first MnO2/MXene hybrids (MnO2/Ti3C2Tx) fabricated by direct chemical synthesis evident a large surface area of 183.8 m2/g compared to pristine Ti3C2Tx (21.1 m2/g).115 Such an increase in surface area enhances the effective contact of electrolyte and active materials by trapping more electrolyte solution. This provides superior pseudocapacitance and improves overall cycling performance. Specific capacitance values of 77.5 and 210.9 Fg-1 are obtained for symmetric supercapacitors of Ti3C2Tx and MnO2/Ti3C2Tx samples respectively at a constant scan rate of 10 mVs-1. At a constant power density of 20 kWKg-1, MnO2/Ti3C2Tx hybrid exhibited an energy density of 12.25 WhKg-1 with a good cyclic stability (88% capacitance retention) after 10000 cycles. Hybrid electrodes of MXene with TiO2, MoO3 have also been developed.108, 112 Hybrid of TiO2/Ti3C2Tx108 exhibited a gravimetric capacitance of 143 Fg-1 retaining ~92% of


Page 20 of 36

Page 21 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

its initial capacitance after 6000 cycles. MoO3, being a highly electrochemically active material increases specific surface area and active sites delivering a maximum capacitance of 151 Fg-1 with 93.7% capacitance retention after 8000 cycles of the charge-discharge process.112 4. Phosphorene Electrodes. Another recently emerging 2D material for energy storage applications is Phosphorene, a single atomic layer of Black phosphorous (BP) analogous to graphene. Phosphorene, a puckered lamellae structure with weakly bonded layers of phosphorous atoms via Van der Waals interactions shows good electrical conductivity, thermodynamical stability, and fast ion diffusivity. These properties make phosphorene an attractive candidate for supercapacitor applications.22,

116

Interestingly, a

flexible solid-state supercapacitor117 based on liquid phase exfoliated phosphorene nanoflakes has been recently developed, which exhibits an impressive volumetric capacitance of 17.78 Fcm-3 (59.3 Fg-1) at 0.1 Vs-1 and excellent rate capacitance while maintaining 1.43 Fcm-3 (4.8 Fg-1) of volumetric capacitance at 10 Vs-1. Phosphorene electrode, even after prolonged (30000) charge/discharge cycles, exhibits high mechanical stability maintaining its crystalline structure as investigated under TEM with corresponding capacitance retention of 71.8%. Red phosphorous (RP), one of the allotropes of phosphorous with high theoretical specific capacitance (similar to BP) 22 has been used to make a hybrid electrode material composed of BP and RP. A simple sonochemical process118 was followed to develop a single elemental hybrid of Black Phosphorous and Red Phosphorus (BP/RP hybrid) and the hybrid electrode was electrochemically tested in 0.1 M KOH electrolyte. The BP/RP hybrid electrode demonstrated a typical EDLC behavior even at higher scan rates and yields specific capacitances of 60.1 Fg-1 and 41.6 Fg-1 at 0.5 Ag-1 and 8 Ag-1 current densities respectively. Hybridisation of BP and RP facilitated a fast and short electronic/ionic transfer leading to high reaction kinetics with good cyclic stability. The hybrid cycled for 2000 cycles retained



83.3% of its initial capacitance, higher than RP. Micro-supercapacitors (MSCs) with a mask assisted interdigital electrode pattern have been fabricated using layer-by-layer stacking of phosphorene nanosheets and electrochemically exfoliated graphene (PG-MSCs) in ionic liquid electrolyte.119 The simplified mask-assisted development of PG-MSCs is scalable for production of serially interconnected MSC pack and provides excellent flexibility as shown in Figure 6 a, b. MSCs provided an excellent electrochemical performance of 9.8 mFcm-2 and volumetric capacitance of 37.5 Fcm-3 at 5 mVs-1 and retained 94% of its initial capacitance under different bending states. The excellent performance of PG-MSCs can be attributed to the strong coupling of phosphorene and graphene nanosheets offering high ionic accommodation, fast transport pathways and restricting graphene restacking due to phosphorene. The graphene serves as a mechanical skeleton providing high speed electron transfer network. The remarkable electrochemical performance endowed by phosphorenebased supercapacitor is an indicative of its potential for widespread applications.

Figure 6 (a) Photograph of 9 serially interconnected PG-MSCs. (b) Flexibility and stability demonstration of PG interdigital electrodes at a highly folded state with inset showing electrodes in unfolding state. Reprinted with permission from ref 119, Copyright 2017 American Chemical Society.

Summary and Outlook. The post graphene era witnesses an explosive development of a breadth of 2D inorganic nanomaterials for many current and future electronic/energy technologies. Electrochemical energy storage via supercapacitors is one of the rapidly evolving thrust area where these materials show uncanny potential towards high energy


Page 22 of 36

Page 23 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

density devices, replacing traditional Li-ion batteries. In this review, we summarize the major advances of 2D inorganic materials such as TMDs, TMOs, TMHs, MXenes, and phosphorene for energy storage in supercapacitors. The use of 2D TMDs as supercapacitor electrode materials is enabled by their large surface areas and variable oxidation states which provide them the capability to store charge via electrical double layers as well as by pseudocapacitance. Moreover, the presence of active edge sites and weak van der Waals gaps between the neighbouring layers in 2D TMDs render promising electrochemical performance. 2D nanostructures of TMOs and TMHs not only provide large surface areas, but a high percentage of surface atoms enriched with redox activities are exposed to electrolyte ions, leading to an enhanced pseudocapacitive performance. Despite significant enhancement in the performance of supercapacitors based on the 2D TMDs, TMOs, and TMHs, the major intrinsic bottleneck that refrain them from widespread practical applications is their low electrical conductivity, which results in inferior pseudocapacitance. To compensate the aforementioned demerits, these materials are either incorporated into highly conductive/capacitive materials like carbon materials and conductive polymers or are subjected to exotic nanomaterials engineering in various form factors such as porous nanostructures, 1D/2D and 3D/2D morphologies, core/shell designs, etc. For example, conducting graphene layers in these hybrids act as fast electron transfer channels, preventing restacking issues, as well as showing high synergic effects with pseudo materials to exhibit high electrochemical performance. Developing porous electrode enhances the surface area and interface contact between electrode/electrolyte, which in turn enhances the specific capacitance/energy density of supercapacitors. In addition to the above approaches, hybrids of 2D TMOs/TMHs, TMOs/TMHs, and TMHs/TMHs have also been developed to achieve advanced supercapacitor electrodes with high redox activity and improved cycle life.



In recent years, supercapacitor research grew considerably due to the emergence of metallic phase in the existing 2D materials or the advent of new metallic materials. For example, 2D TMDs in their metallic (1T) phase have shown exceptional supercapacitor properties, which is benefited by the enhanced conductivity of the network (i.e. 107 times > semiconducting 2H phase) and high hydrophilicity enhancing its contact with aqueous electrolytes. 2D transition metal carbides/nitrides (MXenes) is another emerging class of novel pseudocapacitive electrode materials with extremely high intrinsic electronic/ionic conductivity. The high surface pseudocapacitive activity in MXenes demonstrate very high intercalation capacitance (~1000 Fcm-3) in aqueous electrolytes. Moreover, MXenes filler are playing a key role in enhancing the mechanical property and chemical stability of polymericand metal oxide-based supercapacitor electrodes. Phosphorene, a 2D allotrope of phosphorous, is showing great potential for high performance supercapacitors owing to it excellent electrical conductivity (~300 Sm-1), large interlayer spacing (~3.08A), high thermodynamic stability, and fast ion diffusivity. In addition, the outstanding flexibility in phosphorene makes it viable for flexible energy storage devices. A comparison of the electrochemical performance of all 2D materials discussed above is presented in Table 1. Despite a plethora of research conducted in the development of novel 2D nanomaterials discussed in this review, there are still many current and foreseen challenges as well as future directions which might be considered to make these materials viable for commercial energy storage technologies: (i)

Interface-property and performance relationships in 2D hybrids. To leverage the

optimum materials properties from the constituent elements in 2D hybrids, it is imperative to understand their interface relationships that govern the physiochemical properties of the hybrids to exhibit enhanced performances. Even though, a large section of the scientific community observes synergistic effects in terms of enhanced electrochemical performances,


Page 24 of 36

Page 25 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

the legitimate factors responsible for hybrids’ performance are still unknown. For example, how the interface atoms adjust their orientation, crystalline structure, and layer number to exhibit high synergistic effects? What are the fundamental atomistic parameters that define the viability of distinct materials to construct highly compatible hybrids and whether these factors tunable/adjustable to leverage the best materials properties? What are the mechanical/chemical binding principles of 2D materials with interacting materials and how the

interface

chemistry

influences

the

overall

electrochemical

performance.

Detailed/advanced studies using in-situ characterizations techniques are required to unveil the fundamentals of hybrid interfaces. (ii)

Metallic 2D materials need further developments. Although metallic 2D materials

such as 1T TMDs and MXenes show enormous potential towards high energy density supercapacitors owing to their intrinsically high electrical conductivity as well as versatile transition metal chemistry to exhibit pseudocapacitive charge storage, their research is still at the tip of the iceberg. 1T TMDs fabrication is generally accompanied with the formation of 2H counterparts or an easy phase transition occurs from 1T to 2H phase in some cases. Therefore, proper fabrication methods are required to achieve stable/purely 1T phase to access their real performance. MXenes growth technique use toxic acids (e.g. hydrofluoric acid (HF)) resulting in arbitrary functionalization which overshadow their real performance. Hence, an acid-free growth of MXenes and MXenes without surface functionalization is required to leverage their intrinsic performance as electrode materials. Furthermore, the behavior of metallic TMDs and MXenes with other capacitive materials such as conductive polymers, carbon materials, transition metal oxides/nitrides in the form of hybrids/composites is less known. Such hybrids are expected to promote the electrons/ions conduction pathways by manifold to achieve high performance supercapacitors.



(iii)

Page 26 of 36

Need for novel electrolytes and stability issues. The limited number of aqueous/non-

aqueous electrolytes known to the scientific community are becoming obsolete with the advent of an array of novel 2D nanomaterials due to the novel physiochemical properties of the surface atoms of newly developed 2D electrode materials. For example, MXenes are prone to easy oxidization in various aqueous electrolytes, which results in an increase of resistance and capacitance decay during cycling tests.98 Hence, there is a parallel need to develop compatible electrolytes along with the development of novel 2D electrode materials. On the other hand, novel electrodes like phosphorene face stability issues under ambient environments and require inert environment to assemble supercapacitors.120 Serious research efforts are needed to unveil and mitigate this limitation. Proper encapsulation or functionalization of phosphorene while maintaining its electrochemical entity could be one of the possible approaches to alleviate the stability issues.

Table 1. Various 2D materials and their supercapacitor performances 2D family

Active Material

TMDs

MoS2 nanowall films MoS2/MWCNT nanocomposite MoS2rGO/MWCNT

TMDs/ Carbonaceou s hybrids

TMDs/ Conductive Polymers (CPs) hybrids

Capacitance/Scan rate

100 Fg-1 / 1 mVs-1 452 Fg-1 / 1 Ag-1 ~6.2 Fcm-3 / 0.07 Acm-3

Rate capability

Energy Density

Cycle test Capacitance retention (%)/cycles -

Ref

-

-

73.71% from 1 to 10 Ag-1 61 % from 0.07 to 3.3 Acm-3 ~50% from 2 to 20 Ag-1

-

95.8 / 1000

47

-

~99 / 7000

48

78.8 Whkg-1 at 284.1 Wkg-1

90 / 5000

49

82% from 0.5 to 30 Ag-1

-

79 / 6000

52

32

Flower-like MoS2/GNS

320 Fg-1 / 2 Ag-1; ASC– 142 Fg-1 / 2 mVs-1

Tubular MoS2/PANI nanowires MoS2 nanosheets @PANI nanoneedle arrays

552 Fg-1 / 0.5 Ag-1

853 Fg-1 / 1 Ag-1

-

106 Whkg-1 at 106 kWkg-1

83 / 4000

24

Metallic 1T-WS2 nanoribbons Metallic 1T-MoS2

2813 µFcm-2 / 0.5 Am-2 ~400 to 700 Fcm-3

-

-

~34 / 2000

44

> 93-97 / 5000

16

-


0.016

Page 27 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

Metallic TMDs

nanosheets VS2 nanosheets MnO2 nanosheets

δ-MnO2 nanosheets δMnO2/Graphene hybrid Transition Metal Oxides

e-Fe3O4@RGO sheets Ultrathin Co3O4 nanosheets 2D Co3O4 by 3D interconnected nanoflakes Co3O4 nanosheet arrays Porous NiO hollow spheres β-Co(OH)2

α-Ni(OH)2 nanosheets Ni(OH)2 nanoplates Transition Metal Hydroxides

Ni50Co50-LDH

Ni(OH)2/Co(OH)2 ultrathin Ni(OH)2MnO2 hybrid nanosheet arrays Layered Ti3C2 Ti3C2 clay MXene

76% from 2 to 50 mVs-1

267 Fg-1 / 0.2 Ag-1 329 Fg-1 / 0.5 Ag-1

1782 Fg-1 / 5 mAcm; ASC – 108 Fg-1 / 5 mAcm-2 1500 Fg-1 / 1 Ag-1 2

-1

2735 Fg / 2 Ag

43

97.2 Whkg-1

> 97 / 10000

18

-

-

77.9% from 0.2 to 10 Ag-1

18.64 Whkgat 12.6 kWkg-1 85 Whkg-1 at 2.4 kWkg-1 134 Whkg-1 at 1111 Wkg-1 15.4 Whkg-1 at 0.8 kWkg-

90% from 0.5 to 10 Ag-1 51% from 5 to 30 mAcm-2 55.2% from 1 to 10 Ag-1

53.78% from 2 to 10 Ag-1 -

600 Fg-1 / 10 Ag-1 2028 Fg-1 / 5 mVs-1

-

4172 Fg-1 / 1 Ag-1 1335 Fg-1 / 2.8 Ag-1

1537 Fg-1 / 0.5 Ag-1; ASC– 107.8 Fg-1 / 1 mAcm-2 762 Cg−1 / 1 Ag-1 2628 Fg-1 / 3 Ag-1; ASC – 538 Fg-1 / 1.4 Ag-1 340 Fcm-3 900 Fcm-3 / 20 mVs1 ; 245 Fg-1 / 2 mVs-1

Ti3C2Tx@ Silver plated Nylon Ti3C2Tx/PVA film

530 Fcm-3 / 2 mVs-1

Ti3C2Tx flakes

100 / 1000

-

69

92 / 7000

63

95 / 1000

75

> 90 / 2000

76

99.3 / 2000

78

99 / 3000

79

1

1

-1

499 Fg-1 / 2 mVs-1 520 Fcm-3 and 325 Fg-1 / 2 mVs-1 579 mFcm-2 / 2 mVs-1 ~ 357 F cm-3 / 20 mVs-1 328 mFcm-2 / 2 mVs-1

Ti3C2 nanoflakes d-Ti3C2 Ti3C2

Flexible MXene

4760 µFcm-2 ( 317 Fcm-3 ) / 0.1 Am-2 774 Fg-1 / 0.1 Ag-1; ASC - 175 Fg-1 at 0.1 Ag-1 ≥ 300 Fg-1

Whcm-3 at 0.62 Wcm-3 -

64.23% from 1 to 16 Ag-1 71.40% from 2.8 to 45.7 Ag-1 76.9% from 0.5 to 10 Ag-1

19.44 Whkg−1 98.9 Whkg-1 at 17.981 kWkg-1 -

-

80

93.2 / 10000

90

98.5 / 2000

20

37 Whkg-1 at 10 kWkg-1

100 / 2000

91

33.7 Whkg-1 at 5.4 kWkg-

80.3 / 1000

92

1

50.53% from 3 to 20 Ag-1

101.3 Whg−1 186 Whkg-1 at 778 Wkg-1

ASC- 76% after 3000

93 94

-

-

100 / 10000 100 / 10000

98 99

-

-

100 / 10000 100 / 10000

100 101

-

-

98 / 10000

102

-

-

100 / 10000

106

-

7.3 µWhcm−2 at 132 µWcm−2 -

~100 / 10000

107

~85 / 10000

113

1. 100 / 10000 2. 109 / 10000

114

48.73% from 2 to 100 mVs1

1.Ti3C2Tx/SWCN T composite

-3

-

1. 345 Fcm / 5 Ag ;

1

1. ~87% from 5 to 10 Ag-1.


-


MXene Composites

paper. 2.Ti3C2Tx/rGO composite paper MnO2/Ti3C2Tx hybrid

2. 435 Fcm-3 / 2 mVs-1

Page 28 of 36

2. 74% from 2 to 200 mVs1

-1

-

210.9 Fg / 10 mVs 1 ; 212.1 Fg-1 / 1 Ag-1

83% from 1 to 40 Ag-1

143 Fg-1 / 5 mVs-1

82% from 5 to 200 mVs-1 -

TiO2/Ti3C2 nanocomposite MoO3/Ti3C2Tx composite Phosphorene nanoflakes BP/RP hybrid

17.78 Fcm-3 (59.3 Fg-1) / 0.1 Vs-1 60.1 Fg-1 / 0.5 Ag-1

Phosphorene nanosheets

9.8 mFcm-2 or 37.5 Fcm-3 / 5 mVs-1

151 Fg-1 / 2 mVs-1

Phosphorene

~9% from 0.1 to 10 Vs-1 69.2%from 0.5 to 8 Ag-1 -

12.25 Whkg1 at 20 kWkg-1 -

88 / 10000

115

92 / 6000

108

-

93.7 / 8000

112

-

71.8 / 30000

117

-

83.3 / 2000

118

89.5 / 2000

119

11.6 mWhcm-3

AUTHOR INFORMATION Corresponding Author *

Email: [email protected]

Notes The authors declare no competing financial interest. Biographies Kowsik Sambath Kumar is a Ph.D. student in Materials Science and Engineering Department at the University of Central Florida (UCF) and working under the supervision of Dr. Jayan Thomas. He received his B.Tech in Chemical and Electrochemical Engineering from CSIR-CECRI, India in 2016. His current research focuses on the development of nanostructured materials for energy storage devices. Nitin Choudhary is a postdoctoral researcher at the NanoScience Technology Center (NSTC) of the University of Central Florida, USA. He graduated from the Indian Institute of Technology (IIT), India in the field of experimental physics/nanotechnology. He is currently working in the field of low-dimensional materials for next-generation electronics and energy applications.


Page 29 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

Yeonwoong Jung is an assistant professor at NanoScience Technology Center (NSTC), Materials Science and Engineering, and Electrical and Computer Engineering at the University of Central Florida. He received his Ph.D. in materials science and engineering from the University of Pennsylvania, Philadelphia, USA. He joined UCF in 2015 after completing his postdoctoral training at Yale University. His research group at UCF currently focuses on developing 2D layered materials and their hybrid systems for electronics, energy, and environmental applications. Jayan Thomas is an associate professor at NanoScience Technology Center (NSTC), College of Optics and Photonics (CREOL) and College of Engineering and Computer Science at the University of Central Florida. After receiving his Ph.D. from Cochin University of Science and Technology in India, he joined the College of Optical Sciences, the University of Arizona in 2001 as a research faculty. He moved to UCF in 2011 and is currently working on the development of energy harvesting devices, wearables energy devices, solar cells, and photorefractive polymers. ACKNOWLEDGEMENTS JT acknowledges the University of Central Florida "Reach for the stars" award for the financial support. REFERENCES (1)

Yu, Z. A.; Li, C.; Abbitt, D.; Thomas, J. Flexible, sandwich-like Ag-nanowire/PEDOT:PSSnanopillar/MnO2 high performance supercapacitors. J Mater Chem A 2014, 2, 10923-10929. (2) Simon, P.; Gogotsi, Y. Materials for electrochemical capacitors. Nat Mater 2008, 7, 845-854. (3) Yu, Z. N.; Duong, B.; Abbitt, D.; Thomas, J. Highly ordered MnO2 nanopillars for enhanced supercapacitor performance. Adv Mater 2013, 25, 3302-3306. (4) Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D. Challenges in the development of advanced Li-ion batteries: a review. Energ Environ Sci 2011, 4, 3243-3262. (5) Scrosati, B.; Garche, J. Lithium batteries: Status, prospects and future. J Power Sources 2010, 195, 2419-2430. (6) Miller, J. R.; Simon, P. Electrochemical capacitors for energy management. Science Magazine 2008, 321, 651-652.



(7) Yu, Z. N.; Tetard, L.; Zhai, L.; Thomas, J. Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions. Energ Environ Sci 2015, 8, 702-730. (8) Choudhary, N.; Li, C.; Moore, J.; Nagaiah, N.; Zhai, L.; Jung, Y.; Thomas, J. Asymmetric supercapacitor electrodes and devices. Adv Mater 2017, 29 , 1-30. (9) Zhang, L. L.; Zhou, R.; Zhao, X. S. Graphene-based materials as supercapacitor electrodes. J Mater Chem 2010, 20, 5983-5992. (10) Ke, Q.; Wang, J. Graphene-based materials for supercapacitor electrodes–A review. Journal of Materiomics 2016, 2, 37-54. (11) Lei, Z. B.; Sun, X. X.; Wang, H. J.; Liu, Z. H.; Zhao, X. S. Platelet CMK-5 as an excellent mesoporous carbon to enhance the pseudocapacitance of polyaniline. Acs Appl Mater Inter 2013, 5, 7501-7508. (12) Wang, G. P.; Zhang, L.; Zhang, J. J. A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev 2012, 41, 797-828. (13) Raccichini, R.; Varzi, A.; Passerini, S.; Scrosati, B. The role of graphene for electrochemical energy storage. Nat Mater 2015, 14, 271-279. (14) Choi, W.; Choudhary, N.; Han, G. H.; Park, J.; Akinwande, D.; Lee, Y. H. Recent development of two-dimensional transition metal dichalcogenides and their applications. Mater Today 2017, 20, 116-130. (15) Yang, Y.; Fei, H. L.; Ruan, G. D.; Xiang, C. S.; Tour, J. M. Edge-oriented MoS2 nanoporous films as flexible electrodes for hydrogen evolution reactions and supercapacitor devices. Adv Mater 2014, 26, 8163-8168. (16) Acerce, M.; Voiry, D.; Chhowalla, M. Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials. Nat Nanotechnol 2015, 10, 313-318. (17) Jiang, Y. Q.; Chen, L. Y.; Zhang, H. Q.; Zhang, Q.; Chen, W. F.; Zhu, J. K.; Song, D. M. Twodimensional Co3O4 thin sheets assembled by 3D interconnected nanoflake array framework structures with enhanced supercapacitor performance derived from coordination complexes. Chem Eng J 2016, 292, 1-12. (18) Shi, S.; Xu, C.; Yang, C.; Chen, Y.; Liu, J.; Kang, F. Flexible asymmetric supercapacitors based on ultrathin two-dimensional nanosheets with outstanding electrochemical performance and aesthetic property. Sci Rep-Uk 2013, 3, 1-8. (19) Zhu, L. L.; Peh, C. K. N.; Zhu, T.; Lim, Y. F.; Ho, G. W. Bifunctional 2D-on-2D MoO3 nanobelt/Ni(OH)2 nanosheets for supercapacitor-driven electrochromic energy storage. J Mater Chem A 2017, 5, 8343-8351. (20) Zhu, Y. Q.; Cao, C. B.; Tao, S.; Chu, W. S.; Wu, Z. Y.; Li, Y. D. Ultrathin nickel hydroxide and oxide nanosheets: synthesis, characterizations and excellent supercapacitor performances. Sci RepUk 2014, 4, 1-7. (21) Naguib, M.; Kurtoglu, M.; Presser, V.; Lu, J.; Niu, J. J.; Heon, M.; Hultman, L.; Gogotsi, Y.; Barsoum, M. W. Two-dimensional nanocrystals produced by exfoliation of Ti3AlC2. Adv Mater 2011, 23, 4248-4253. (22) Park, C. M.; Kim, J. H.; Kim, H.; Sohn, H. J. Li-alloy based anode materials for Li secondary batteries. Chem Soc Rev 2010, 39, 3115-3141. (23) Choudhary, N.; Li, C.; Chung, H. S.; Moore, J.; Thomas, J.; Jung, Y. High-performance onebody core/shell nanowire supercapacitor enabled by conformal growth of capacitive 2D WS2 layers. Acs Nano 2016, 10, 10726-10735. (24) Zhu, J. X.; Sun, W. P.; Yang, D.; Zhang, Y.; Hoon, H. H.; Zhang, H.; Yan, Q. Y. Multifunctional architectures constructing of PANI nanoneedle arrays on MoS2 thin nanosheets for high-energy supercapacitors. Small 2015, 11, 4123-4129. (25) Nagaraju, D. H.; Wang, Q. X.; Beaujuge, P.; Alshareef, H. N. Two-dimensional heterostructures of V2O5 and reduced graphene oxide as electrodes for high energy density asymmetric supercapacitors. J Mater Chem A 2014, 2, 17146-17152.


Page 30 of 36

Page 31 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

(26) Fan, Z. J.; Yan, J.; Wei, T.; Zhi, L. J.; Ning, G. Q.; Li, T. Y.; Wei, F. Asymmetric supercapacitors based on graphene/MnO2 and activated carbon nanofiber electrodes with high power and energy density. Adv Funct Mater 2011, 21, 2366-2375. (27) Yan, J.; Fan, Z. J.; Sun, W.; Ning, G. Q.; Wei, T.; Zhang, Q.; Zhang, R. F.; Zhi, L. J.; Wei, F. Advanced ssymmetric supercapacitors based on Ni(OH)2/graphene and porous graphene electrodes with high energy density. Adv Funct Mater 2012, 22, 2632-2641. (28) Cao, L. J.; Yang, S. B.; Gao, W.; Liu, Z.; Gong, Y. J.; Ma, L. L.; Shi, G.; Lei, S. D.; Zhang, Y. H.; Zhang, S. T.; Vajtai, R.; Ajayan, P. M. Direct laser-patterned micro-supercapacitors from paintable MoS2 films. Small 2013, 9, 2905-2910. (29) Muller, G. A.; Cook, J. B.; Kim, H. S.; Tolbert, S. H.; Dunn, B. High performance pseudocapacitor based on 2D layered metal chalcogenide nanocrystals. Nano Lett 2015, 15, 19111917. (30) Koroteev, V. O.; Kuznetsova, I. V.; Kurenya, A. G.; Kanygin, M. A.; Fedorovskaya, E. O.; Mikhlin, Y. L.; Chuvilin, A. L.; Bulusheva, L. G.; Okotrub, A. V. Enhanced supercapacitance of vertically aligned multi-wall carbon nanotube array covered by MoS2 nanoparticles. Phys Status Solidi B 2016, 253, 2451-2456. (31) Choudhary, N.; Patel, M.; Ho, Y. H.; Dahotre, N. B.; Lee, W.; Hwang, J. Y.; Choi, W. Directly deposited MoS2 thin film electrodes for high performance supercapacitors. J Mater Chem A 2015, 3, 24049-24054. (32) Soon, J. M.; Loh, K. P. Electrochemical double-layer capacitance of MoS2 nanowall films. Electrochem Solid St 2007, 10, A250-A254. (33) Zhang, F.; Tang, Y. B.; Liu, H.; Ji, H. Y.; Jiang, C. L.; Zhang, J.; Zhang, X. L.; Lee, C. S. Uniform incorporation of flocculent molybdenum disulfide nanostructure into three-dimensional porous graphene as an anode for high-performance lithium ion batteries and hybrid supercapacitors. Acs Appl Mater Inter 2016, 8, 4691-4699. (34) Ge, Y.; Jalili, R.; Wang, C.; Zheng, T.; Chao, Y.; Wallace, G. G. A robust free-standing MoS2/poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonate) film for supercapacitor applications. Electrochimica Acta 2017, 235, 348-355. (35) Yang, M.; Jeong, J. M.; Huh, Y. S.; Choi, B. G. High-performance supercapacitor based on three-dimensional MoS2/graphene aerogel composites. Compos Sci Technol 2015, 121, 123-128. (36) Yang, C.; Chen, Z. X.; Shakir, I.; Xu, Y. X.; Lu, H. B. Rational synthesis of carbon shell coated polyaniline/MoS2 monolayer composites for high-performance supercapacitors. Nano Res 2016, 9, 951-962. (37) Bissett, M. A.; Kinloch, I. A.; Dryfe, R. A. W., Characterization of MoS2-graphene composites for high-performance coin cell supercapacitors. Acs Appl Mater Inter 2015, 7, 17388-17398. (38) Patil, S.; Harle, A.; Sathaye, S.; Patil, K. Development of a novel method to grow mono-/fewlayered MoS2 films and MoS2-graphene hybrid films for supercapacitor applications. Crystengcomm 2014, 16, 10845-10855. (39) Huang, K. J.; Wang, L.; Liu, Y. J.; Liu, Y. M.; Wang, H. B.; Gan, T.; Wang, L. L. Layered MoS2graphene composites for supercapacitor applications with enhanced capacitive performance. Int J Hydrogen Energ 2013, 38, 14027-14034. (40) Wang, J.; Wu, Z. C.; Hu, K. H.; Chen, X. Y.; Yin, H. B. High conductivity graphene-like MoS2/polyaniline nanocomposites and its application in supercapacitor. J Alloy Compd 2015, 619, 3843. (41) Ma, G. F.; Peng, H.; Mu, J. J.; Huang, H. H.; Zhou, X. Z.; Lei, Z. Q. In situ intercalative polymerization of pyrrole in graphene analogue of MoS2 as advanced electrode material in supercapacitor. J Power Sources 2013, 229, 72-78. (42) Wang, J.; Wu, Z. C.; Yin, H. B.; Li, W.; Jiang, Y. Poly(3,4-ethylenedioxythiophene)/MoS2 nanocomposites with enhanced electrochemical capacitance performance. Rsc Adv 2014, 4, 5692656932.



(43) Feng, J.; Sun, X.; Wu, C. Z.; Peng, L. L.; Lin, C. W.; Hu, S. L.; Yang, J. L.; Xie, Y. Metallic fewlayered VS2 ultrathin nanosheets: high two-dimensional conductivity for in-plane supercapacitors. J Am Chem Soc 2011, 133, 17832-17838. (44) Khalil, A.; Liu, Q.; He, Q.; Xiang, T.; Liu, D.; Wang, C.; Fang, Q.; Song, L. Metallic 1T-WS2 nanoribbons as highly conductive electrodes for supercapacitors. RSC Adv 2016, 6, 48788-48791. (45) Yang, X.; Niu, H.; Jiang, H.; Wang, Q.; Qu, F. A high energy density all-solid-state asymmetric supercapacitor based on MoS2/graphene nanosheets and MnO2/graphene hybrid electrodes. J Mater Chem A 2016, 4, 11264-11275. (46) da Silveira Firmiano, E. G.; Rabelo, A. C.; Dalmaschio, C. J.; Pinheiro, A. N.; Pereira, E. C.; Schreiner, W. H.; Leite, E. R. Supercapacitor electrodes obtained by directly bonding 2D MoS2 on reduced graphene oxide. Adv Energy Mater 2014, 4, 1-8. (47) Huang, K. J.; Wang, L.; Zhang, J. Z.; Wang, L. L.; Mo, Y. P. One-step preparation of layered molybdenum disulfide/multi-walled carbon nanotube composites for enhanced performance supercapacitor. Energy 2014, 67, 234-240. (48) Sun, G. Z.; Zhang, X.; Lin, R. Z.; Yang, J.; Zhang, H.; Chen, P. Hybrid fibers made of molybdenum disulfide, reduced graphene oxide, and multi-walled carbon nanotubes for solid-state, flexible, asymmetric supercapacitors. Angew Chem Int Edit 2015, 54, 4651-4656. (49) Yang, X.; Niu, H.; Jiang, H.; Wang, Q.; Qu, F. Y. A high energy density all-solid-state asymmetric supercapacitor based on MoS2/graphene nanosheets and MnO2/graphene hybrid electrodes. J Mater Chem A 2016, 4, 11264-11275. (50) Kim, J.; Lee, J.; You, J.; Park, M. S.; Al Hossain, M. S.; Yamauchi, Y.; Kim, J. H. Conductive polymers for next-generation energy storage systems: recent progress and new functions. Mater Horiz 2016, 3, 517-535. (51) Shown, I.; Ganguly, A.; Chen, L. C.; Chen, K. H. Conducting polymer-based flexible supercapacitor. Energy Sci Eng 2015, 3, 2-26. (52) Ren, L. J.; Zhang, G. N.; Yan, Z.; Kang, L. P.; Xu, H.; Shi, F.; Lei, Z. B.; Liu, Z. H. Threedimensional tubular MoS2/PANI hybrid electrode for high rate performance supercapacitor. Acs Appl Mater Inter 2015, 7, 28294-28302. (53) Wang, X.; Kalali, E. N.; Wang, D. Y. An in situ polymerization approach for functionalized MoS2/nylon-6 nanocomposites with enhanced mechanical properties and thermal stability. J Mater Chem A 2015, 3, 24112-24120. (54) Huang, K. J.; Wang, L.; Liu, Y. J.; Wang, H. B.; Liu, Y. M.; Wang, L. L. Synthesis of polyaniline/2dimensional graphene analog MoS2 composites for high-performance supercapacitor. Electrochim Acta 2013, 109, 587-594. (55) Wang, D.-W.; Li, F.; Cheng, H.-M. Hierarchical porous nickel oxide and carbon as electrode materials for asymmetric supercapacitor. J Power Sources 2008, 185, 1563-1568. (56) Wei, W.; Cui, X.; Chen, W.; Ivey, D. G. Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chemical Society Reviews 2011, 40, 1697-1721. (57) Subramani, K.; Kowsik, S.; Sathish, M. Facile and scalable ultra–fine cobalt oxide/reduced graphene oxide nanocomposites for high energy asymmetric supercapacitors. Chemistryselect 2016, 1, 3455-3467. (58) Guan, C.; Liu, J.; Wang, Y.; Mao, L.; Fan, Z.; Shen, Z.; Zhang, H.; Wang, J. Iron oxide-decorated carbon for supercapacitor anodes with ultrahigh energy density and outstanding cycling stability. Acs Nano 2015, 9, 5198-5207. (59) Jang, J. H.; Kato, A.; Machida, K.; Naoi, K. Supercapacitor performance of hydrous ruthenium oxide electrodes prepared by electrophoretic deposition. Journal of The Electrochemical Society 2006, 153, A321-A328. (60) Giardi, R.; Porro, S.; Topuria, T.; Thompson, L.; Pirri, C. F.; Kim, H.-C. One-pot synthesis of graphene-molybdenum oxide hybrids and their application to supercapacitor electrodes. Applied Materials Today 2015, 1, 27-32.


Page 32 of 36

Page 33 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

(61) Pan, X. X.; Chen, X. M.; Li, Y.; Yu, Z. N. Facile synthesis of Co3O4 nanosheets electrode with ultrahigh specific capacitance for electrochemical supercapacitors. Electrochim Acta 2015, 182, 1101-1106. (62) Yuan, C. Z.; Zhang, X. G.; Su, L. H.; Gao, B.; Shen, L. F. Facile synthesis and self-assembly of hierarchical porous NiO nano/micro spherical superstructures for high performance supercapacitors. J Mater Chem 2009, 19, 5772-5777. (63) Peng, L. L.; Peng, X.; Liu, B. R.; Wu, C. Z.; Xie, Y.; Yu, G. H. Ultrathin two-dimensional MnO2/graphene hybrid nanostructures for high-performance, flexible planar supercapacitors. Nano Lett 2013, 13, 2151-2157. (64) Zhi, J.; Yang, C.; Lin, T.; Cui, H.; Wang, Z.; Zhang, H.; Huang, F. Flexible all solid state supercapacitor with high energy density employing black titania nanoparticles as a conductive agent. Nanoscale 2016, 8, 4054-4062. (65) Chen, P. C.; Shen, G. Z.; Shi, Y.; Chen, H. T.; Zhou, C. W. Preparation and characterization of flexible asymmetric supercapacitors based on transition-metal-oxide nanowire/single-walled carbon nanotube hybrid thin-film electrodes. Acs Nano 2010, 4, 4403-4411. (66) He, Y.; Chen, W.; Li, X.; Zhang, Z.; Fu, J.; Zhao, C.; Xie, E. Freestanding three-dimensional graphene/MnO2 composite networks as ultralight and flexible supercapacitor electrodes. Acs Nano 2012, 7, 174-182. (67) Ma, Z.; Shao, G.; Fan, Y.; Wang, G.; Song, J.; Shen, D. Construction of hierarchical α-MnO2 nanowires@ ultrathin δ-MnO2 nanosheets core–shell nanostructure with excellent cycling stability for High-Power Asymmetric Supercapacitor Electrodes. Acs Appl Mater Inter 2016, 8, 9050-9058. (68) Jiang, J. H.; Kucernak, A. Electrochemical supercapacitor material based on manganese oxide: preparation and characterization. Electrochim Acta 2002, 47, 2381-2386. (69) Gao, P.; Metz, P.; Hey, T.; Gong, Y.; Liu, D.; Edwards, D. D.; Howe, J. Y.; Huang, R.; Misture, S. T. The critical role of point defects in improving the specific capacitance of δ-MnO2 nanosheets. Nat Commun 2017, 8, 1-10. (70) Qin, J.; Wu, Z.-S.; Zhou, F.; Dong, Y.; Xiao, H.; Zheng, S.; Wang, S.; Shi, X.; Huang, H.; Sun, C. Simplified fabrication of high areal capacitance all-solid-state micro-supercapacitors based on graphene and MnO2 nanosheets. Chinese Chemical Letters 2017, 1-5. (71) Xia, H.; Wang, Y.; Lin, J. Y.; Lu, L. Hydrothermal synthesis of MnO2/CNT nanocomposite with a CNT core/porous MnO2 sheath hierarchy architecture for supercapacitors. Nanoscale Res Lett 2012, 7, 1-10. (72) Mondal, A. K.; Wang, B.; Su, D. W.; Wang, Y.; Chen, S. Q.; Zhang, X. G.; Wang, G. X. Graphene/MnO2 hybrid nanosheets as high performance electrode materials for supercapacitors. Mater Chem Phys 2014, 143, 740-746. (73) Mendoza-Sanchez, B.; Coelho, J.; Pokle, A.; Nicolosi, V. A 2D graphene-manganese oxide nanosheet hybrid synthesized by a single step liquid-phase co-exfoliation method for supercapacitor applications. Electrochim Acta 2015, 174, 696-705. (74) Liu, D. Q.; Wang, X.; Wang, X. B.; Tian, W.; Liu, J. W.; Zhi, C. Y.; He, D. Y.; Bando, Y.; Golberg, D. Ultrathin nanoporous Fe3O4-carbon nanosheets with enhanced supercapacitor performance. J Mater Chem A 2013, 1, 1952-1955. (75) Qu, Q. T.; Yang, S. B.; Feng, X. L. 2D sandwich-like sheets of iron oxide grown on graphene as high energy anode material for supercapacitors. Adv Mater 2011, 23, 5574-5580. (76) Yang, Q.; Lu, Z. Y.; Sun, X. M.; Liu, J. F. Ultrathin Co3O4 nanosheet arrays with high supercapacitive performance. Sci Rep-Uk 2013, 3, 1-7. (77) Lee, K. K.; Chin, W. S.; Sow, C. H. Cobalt-based compounds and composites as electrode materials for high-performance electrochemical capacitors. J Mater Chem A 2014, 2, 17212-17248. (78) Jiang, Y.; Chen, L.; Zhang, H.; Zhang, Q.; Chen, W.; Zhu, J.; Song, D. Two-dimensional Co3O4 thin sheets assembled by 3D interconnected nanoflake array framework structures with enhanced supercapacitor performance derived from coordination complexes. Chem Eng J 2016, 292, 1-12.



(79) Yuan, C. Z.; Yang, L.; Hou, L. R.; Shen, L. F.; Zhang, X. G.; Lou, X. W. Growth of ultrathin mesoporous Co3O4 nanosheet arrays on Ni foam for high-performance electrochemical capacitors. Energ Environ Sci 2012, 5, 7883-7887. (80) Yu, W.; Jiang, X.; Ding, S.; Li, B. Q. Preparation and electrochemical characteristics of porous hollow spheres of NiO nanosheets as electrodes of supercapacitors. J Power Sources 2014, 256, 440448. (81) Gao, Z.; Yang, W. L.; Yan, Y. X.; Wang, J.; Ma, J.; Zhang, X. M.; Xing, B. H.; Liu, L. H. Synthesis and exfoliation of layered α-Co(OH)2 nanosheets and their electrochemical performance for supercapacitors. Eur J Inorg Chem 2013, 2013, 4832-4838. (82) Tang, J.; Liu, D. Q.; Zheng, Y. X.; Li, X. W.; Wang, X. H.; He, D. Y. Effect of Zn-substitution on cycling performance of α -Co(OH)2 nanosheet electrode for supercapacitors. J Mater Chem A 2014, 2, 2585-2591. (83) Lu, Z. Y.; Chang, Z.; Zhu, W.; Sun, X. M. β-phased Ni(OH)2 nanowall film with reversible capacitance higher than theoretical Faradic capacitance. Chem Commun 2011, 47, 9651-9653. (84) Sun, W. P.; Rui, X. H.; Ulaganathan, M.; Madhavi, S.; Yan, Q. Y. Few-layered Ni(OH)2 nanosheets for high-performance supercapacitors. J Power Sources 2015, 295, 323-328. (85) Jiang, H.; Zhao, T.; Li, C. Z.; Ma, J. Hierarchical self-assembly of ultrathin nickel hydroxide nanoflakes for high-performance supercapacitors. J Mater Chem 2011, 21, 3818-3823. (86) Zhao, T.; Jiang, H.; Ma, J. Surfactant-assisted electrochemical deposition of α-cobalt hydroxide for supercapacitors. J Power Sources 2011, 196, 860-864. (87) Zhang, J.; Wang, X. C.; Ma, J.; Liu, S.; Yi, X. B. Preparation of cobalt hydroxide nanosheets on carbon nanotubes/carbon paper conductive substrate for supercapacitor application. Electrochim Acta 2013, 104, 110-116. (88) Huang, J. C.; Xu, P. P.; Cao, D. X.; Zhou, X. B.; Yang, S. N.; Li, Y. J.; Wang, G. L. Asymmetric supercapacitors based on β-Ni(OH)2 nanosheets and activated carbon with high energy density. J Power Sources 2014, 246, 371-376. (89) Wang, R. T.; Yan, X. B.; Lang, J. W.; Zheng, Z. M.; Zhang, P. A hybrid supercapacitor based on flower-like Co(OH)(2) and urchin-like VN electrode materials. J Mater Chem A 2014, 2, 12724-12732. (90) Gao, S.; Sun, Y. F.; Lei, F. C.; Liang, L.; Liu, J. W.; Bi, W. T.; Pan, B. C.; Xie, Y. Ultrahigh energy density realized by a single-layer β-Co(OH)2 all-solid-state asymmetric supercapacitor. Angew Chem Int Edit 2014, 53, 12789-12793. (91) Wang, H. L.; Casalongue, H. S.; Liang, Y. Y.; Dai, H. J. Ni(OH)2 Nanoplates grown on graphene as advanced electrochemical pseudocapacitor materials. J Am Chem Soc 2010, 132, 7472-7477. (92) Li, R.; Hu, Z.; Shao, X.; Cheng, P.; Li, S.; Yu, W.; Lin, W.; Yuan, D. Large scale synthesis of NiCo layered double hydroxides for superior asymmetric electrochemical capacitor. Sci Rep-Uk 2016, 6, 18737, 1-9. (93) Nguyen, T.; Boudard, M.; Carmezim, M. J.; Montemor, M. F. Layered Ni(OH)2-Co(OH)2 films prepared by electrodeposition as charge storage electrodes for hybrid supercapacitors. Sci Rep-Uk 2017, 7, 1-10. (94) Chen, H.; Hu, L. F.; Yan, Y.; Che, R. C.; Chen, M.; Wu, L. M. One-step fabrication of ultrathin porous nickel hydroxide-manganese dioxide hybrid nanosheets for supercapacitor electrodes with excellent capacitive performance. Adv Energy Mater 2013, 3, 1636-1646. (95) Anasori, B.; Xie, Y.; Beidaghi, M.; Lu, J.; Hosler, B. C.; Hultman, L.; Kent, P. R. C.; Gogotsi, Y.; Barsoum, M. W. Two-dimensional, ordered, double transition metals carbides (MXenes). Acs Nano 2015, 9, 9507-9516. (96) Kurtoglu, M.; Naguib, M.; Gogotsi, Y.; Barsoum, M. W. First principles study of twodimensional early transition metal carbides. Mrs Commun 2012, 2, 133-137. (97) Lei, J. C.; Zhang, X.; Zhou, Z. Recent advances in MXene: preparation, properties, and applications. Front Phys-Beijing 2015, 10, 276-286.


Page 34 of 36

Page 35 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

(98) Lukatskaya, M. R.; Mashtalir, O.; Ren, C. E.; Dall'Agnese, Y.; Rozier, P.; Taberna, P. L.; Naguib, M.; Simon, P.; Barsoum, M. W.; Gogotsi, Y. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science 2013, 341, 1502-1505. (99) Ghidiu, M.; Lukatskaya, M. R.; Zhao, M. Q.; Gogotsi, Y.; Barsoum, M. W. Conductive twodimensional titanium carbide 'clay' with high volumetric capacitance. Nature 2014, 516, 78-81. (100) Hu, M. M.; Li, Z. J.; Zhang, H.; Hu, T.; Zhang, C.; Wu, Z.; Wang, X. H. Self-assembled Ti3C2Tx MXene film with high gravimetric capacitance. Chem Commun 2015, 51, 13531-13533. (101) Dall'Agnese, Y.; Lukatskaya, M. R.; Cook, K. M.; Taberna, P. L.; Gogotsi, Y.; Simon, P. High capacitance of surface-modified 2D titanium carbide in acidic electrolyte. Electrochem Commun 2014, 48, 118-122. (102) Lin, S. Y.; Zhang, X. T. Two-dimensional titanium carbide electrode with large mass loading for supercapacitor. J Power Sources 2015, 294, 354-359. (103) Krishnamoorthy, K.; Pazhamalai, P.; Sahoo, S.; Kim, S. J. Titanium carbide sheet based high performance wire type solid state supercapacitors. J Mater Chem A 2017, 5, 5726-5736. (104) Hu, H. B.; Hua, T. An easily manipulated protocol for patterning of MXenes on paper for planar micro-supercapacitors. J Mater Chem A 2017, 5, 19639-19648. (105) Li, H. Y.; Hou, Y.; Wang, F. X.; Lohe, M. R.; Zhuang, X. D.; Niu, L.; Feng, X. L. Flexible all-solidstate supercapacitors with high volumetric capacitances boosted by solution processable MXene and electrochemically exfoliated graphene. Adv Energy Mater 2017, 7, 1-6. (106) Peng, Y. Y.; Akuzum, B.; Kurra, N.; Zhao, M. Q.; Alhabe, M.; Anasori, B.; Kumbur, E. C.; Alshareef, H. N.; Ger, M. D.; Gogotsi, Y. All-MXene (2D titanium carbide) solid-state microsupercapacitors for on-chip energy storage. Energ Environ Sci 2016, 9, 2847-2854. (107) Hu, M.; Li, Z.; Li, G.; Hu, T.; Zhang, C.; Wang, X. All-solid-state flexible fiber-based MXene supercapacitors. Advanced Materials Technologies, 2017, 1700143, 1-6. (108) Zhu, J. F.; Tang, Y.; Yang, C. H.; Wang, F.; Cao, M. J. Composites of TiO2 nanoparticles deposited on Ti3C2 MXene nanosheets with enhanced electrochemical performance. J Electrochem Soc 2016, 163, A785-A791. (109) Boota, M.; Anasori, B.; Voigt, C.; Zhao, M. Q.; Barsoum, M. W.; Gogotsi, Y. Pseudocapacitive electrodes produced by oxidant-free polymerization of pyrrole between the layers of 2D titanium carbide (MXene). Adv Mater 2016, 28, 1517-1522. (110) Zhao, C. J.; Wang, Q.; Zhang, H.; Passerini, S.; Qian, X. Z. Two-dimensional titanium carbide/RGO composite for high-performance supercapacitors. Acs Appl Mater Inter 2016, 8, 1566115667. (111) Dall'Agnese, Y.; Rozier, P.; Taberna, P. L.; Gogotsi, Y.; Simon, P. Capacitance of twodimensional titanium carbide (MXene) and MXene/carbon nanotube composites in organic electrolytes. J Power Sources 2016, 306, 510-515. (112) Zhu, J. F.; Lu, X.; Wang, L. Synthesis of a MoO3/Ti3C2Tx composite with enhanced capacitive performance for supercapacitors. Rsc Adv 2016, 6, 98506-98513. (113) Ling, Z.; Ren, C. E.; Zhao, M. Q.; Yang, J.; Giammarco, J. M.; Qiu, J. S.; Barsoum, M. W.; Gogotsi, Y. Flexible and conductive MXene films and nanocomposites with high capacitance. P Natl Acad Sci USA 2014, 111, 16676-16681. (114) Zhao, M. Q.; Ren, C. E.; Ling, Z.; Lukatskaya, M. R.; Zhang, C. F.; Van Aken, K. L.; Barsoum, M. W.; Gogotsi, Y. Flexible MXene/carbon nanotube composite paper with high volumetric capacitance. Adv Mater 2015, 27, 339-345. (115) Rakhi, R. B.; Ahmed, B.; Anjum, D.; Alshareef, H. N. Direct chemical synthesis of MnO2 nanowhiskers on transition metal carbide surfaces for supercapacitor applications. ACS Appl Mater Inter 2016, 8, 18806-18814. (116) Castellanos-Gomez, A.; Vicarelli, L.; Prada, E.; Island, J. O.; Narasimha-Acharya, K. L.; Blanter, S. I.; Groenendijk, D. J.; Buscema, M.; Steele, G. A.; Alvarez, J. V.; Zandbergen, H. W.; Palacios, J. J.; van der Zant, H. S. J. Isolation and characterization of few-layer black phosphorus. 2d Mater 2014, 1, 1-19.



(117) Hao, C. X.; Yang, B. C.; Wen, F. S.; Xiang, J. Y.; Li, L.; Wang, W. H.; Zeng, Z. M.; Xu, B.; Zhao, Z. S.; Liu, Z. Y.; Tian, Y. J. Flexible all-solid-state supercapacitors based on liquid-exfoliated blackphosphorus nanoflakes. Adv Mater 2016, 28, 3194-3201. (118) Chen, X. H.; Xu, G. G.; Ren, X. H.; Li, Z. J.; Qi, X.; Huang, K.; Zhang, H.; Huang, Z. Y.; Zhong, J. X. A black/red phosphorus hybrid as an electrode material for high-performance Li-ion batteries and supercapacitors. J Mater Chem A 2017, 5, 6581-6588. (119) Xiao, H.; Wu, Z.-S.; Chen, L.; Zhou, F.; Zheng, S.; Ren, W.; Cheng, H.-M.; Bao, X. One-step device fabrication of phosphorene and graphene interdigital micro-supercapacitors with high energy density. Acs Nano 2017, 11, 7284-7292. (120) Pei, J. J.; Gai, X.; Yang, J.; Wang, X. B.; Yu, Z. F.; Choi, D. Y.; Luther-Davies, B.; Lu, Y. R. Producing air-stable monolayers of phosphorene and their defect engineering. Nat Commun 2016, 7, 1-8.

Quotes to be highlighted 1. 2D TMDs exhibit high electrochemical activity derived from their edge sites, which offer large energy storage capability in supercapacitors. 2. 2D TMOs and TMHs are not layered materials like graphene and 2D TMDs, but a similar "2D" terminology is used because of their ultra-small (a few atom) thickness, exhibiting extraordinary properties different from their bulk counterparts. 3. The outstanding performance of the LiF + HCl etched Ti3C2 compared to HF etched Ti3C2 is attributed to pre-intercalated water and smaller size of cation (H+) in the electrolyte.


Page 36 of 36

Recent Advances in Two-Dimensional ... - ACS Publications

Recommend Documents