Nitrogen Doped MXene-Derived Carbon as Graphene Alternative in

Green Energy Applications

Sarah Wittenburg Robert Benke

Dept. of Material Science Eng. Dept. of Material Science Eng.
University of Maryland University of Maryland
College Park, Maryland College Park, Maryland
[email protected] [email protected]

I. Iɴᴛʀᴏᴅᴜcᴛɪᴏɴ accumulate charge via electric double layer capacitance

(EDLC) or pseudocapacitive means [5]. For applications in the
Despite incessant calls to curb climate change, carbon automotive sector, supercapacitors could be used to offset the
emissions from man-made sources remain high. limitations of batteries (including low power density and long
Transportation and electric power were the greatest charging times) and in energy-regenerative systems (such as
contributors to US greenhouse gas (GHG) emissions in 2022, regenerative shock absorbers and brakes) to recover energy
with 28% of total emissions coming from transportation and and increase vehicle range [4]. For context, a report of energy
25% of greenhouse gas emissions coming from electric power storage devices is given in Table 1.
generation with the majority of those emissions arising from
fossil fuel sources [1]. Even with the plurality of renewable Device Specific Specific Specific Capacitance
energy alternatives currently available, improvements in cost Capacitance Energy power retention
and practicality of renewable energy devices and infrastructure
are needed to outcompete fossil fuels in these fields and slash Battery 999.0 106.4 88.8 88.3%
mAh/g (@ Wh/kg W/kg 8000 cycles
global GHG emissions accordingly.
1 A/g) 2 A/g
Energy storage is a particularly prominent issue with Super- 209.0 F/g 59.9 8.6 95% 300 h
renewable energy technologies. In the automotive sector, capacitor (0.1 A/g) Wh/L kW/L
electric vehicles are heavy due to the low gravimetric power
density of Li-ion batteries, and electric vehicles have only Capacito 26.0 pF (1 4.1 2380 N/A
recently gained comparable driving ranges to r kHz) Wh/L MW/L
gasoline-powered vehicles with electric vehicles possessing a
range of 220 miles in 2021 [2]. In the energy sector, solar and Table 1: Typical Energy Storage Device Comparison [4].
wind power are highly weather-dependent and cannot operate
at all times of the day. This leads to times in the day when A particular class of supercapacitors relies on 2D
renewables alone cannot provide a full direct energy supply materials and carbon-based materials for supercapacitor
along with times in the day when energy from renewables is electrodes, including graphene. 2D materials in particular are
over-supplied, as illustrated by the so-called ‘duck curve’ appealing for supercapacitor electrodes because of their
begotten from solar energy harvesting in California [3]. Solar, extremely high specific surface area, which allows for more
wind, geothermal, hydroelectric, and nuclear energy sources space for the formation of electric double layers and thus leads
generate power intermittently depending on weather to increased capacitance [5], [6]. Supercapacitors with
conditions or cannot adjust their power output according to graphene electrodes possess a theoretical capacitance of 550
varying grid-scale power consumption [4]. F/g and are inherently lightweight due to their all-carbon
structure. However, state-of-the art all-carbon capacitors only
With their high power density, rapid charge-discharge achieve capacitances of ~250 F/g and suffer from poor cycling
rates, and long lifetimes, supercapacitors are promising stability, preventing such devices from realizing commercial
devices for solving grid-scale renewable power issues and applications, leaving an open challenge for the creation of 2D
improving electric vehicles. Supercapacitors are devices that or 2D-based electrode materials suitable for practical,
commercial purposes [5], [7]. To take advantage of the supercapacitors, which offer benefits like low cost, long cycle
inherently favorable properties of 2D materials in energy life, and rapid electron transport within the electrode material
storage applications, electrodes with 2D materials must be [10]. The tunable properties of 2D materials allow for the
engineered to achieve higher capacitances close to theoretical optimization of energy storage devices, enhancing their
values and with greater cycling stability. performance in applications like green energy storage and
sustainable power sources.
In this proposal, we discuss the electrochemical properties
of 2D materials on the solid-state physics/nanostructures level For graphene and 2D materials in supercapacitor
to highlight their promise in the field of supercapacitors. We electrodes, electric double-layer capacitance (EDLC) relies on
then propose the engineering of a nitrogen-doped the accumulation of charge in an electric double layer on the
MXene-derived carbon - ordered mesoporous carbon surface of an electrode. For two separated parallel conductors
(N-MDC-OMC) material for supercapacitor electrodes, with electrodes interfaced by an electrolyte, applying a voltage
wherein the material is designed to resist cycling-induced to one electrode will lead to the accumulation of charge on
capacitor degradation and achieve higher capacitances than each electrode until electrostatic equilibrium is reached [4]. As
previously seen for state-of-the-art supercapacitors. Such a the accumulation of a layer of charged particles is vital for
lightweight capacitor system could be utilized in grid-scale EDLC, materials with a high specific area (m2/g), such as 2D
renewable energy storage and automotive applications and materials, are preferred for maximizing the area of the layer
would present a step forward in making renewable energy and thus the charge accumulated [11].
technologies a commercially viable alternative to conventional
energy procurement means across multiple sectors. B. Restacking in 2D materials

Restacking in two-dimensional materials occurs when the

II. Bᴀᴄᴋɢʀᴏᴜɴᴅ individual layers re-aggregate or stack together due to van der
Waals forces holding adjacent layers together, effectively
A. Graphene and other 2D Materials for Green Energy reducing the available surface area for electrochemical
interactions. In graphene, this phenomenon is exacerbated by
Graphene is a flat, two-dimensional sheet characterized π–π stacking interactions between the basal planes of adjacent
by sp² hybridized carbon atoms bonded in a hexagonal pattern. sheets, which can significantly reduce the interlayer spacing.
It stands out among other nano-carbon materials due to its The resulting reduction in surface area limits the efficiency of
exceptional electron mobility, high thermal conductivity, charge storage, which negatively impacts the overall
mechanical strength, chemical stability, large surface area, and performance of supercapacitors, particularly in terms of
transparency to light [8]. Many characteristics of graphene capacitance, charge/discharge rates, and cycle life [10]. This is
arise from the combination of its unique dimensionality and its especially problematic for materials like graphene, where
distinctive electronic band structure, where electrons behave maximizing accessible surface area is critical for high-
akin to relativistic particles [9]. Due to these properties, performance energy storage. Restacking can also hinder the
graphene and a diverse range of graphene-based nano-hybrids movement of ions in the electrolyte, further reducing
have been created and employed in numerous practical conductivity and compromising the stability of the material
applications across different sectors, including electronics, during repeated charge-discharge cycles [7].
biomedical technology, sensor development, energy storage
solutions, and environmental initiatives [8]. Beyond graphene, To fully utilize the potential of these materials, effective
other 2D materials—such as transition metal dichalcogenides, strategies are necessary to counteract restacking. Approaches
MXenes, and black phosphorus—share similar structural to address restacking include introducing intercalants,
characteristics and often exhibit complementary properties. deformation of structure, and integrating 3D porous
frameworks to prevent aggregation and maintain their
In the context of energy storage, graphene and its 2D beneficial properties [10]. A particularly effective method
counterparts have emerged as particularly promising materials involves incorporating nanomaterials as spacers between
for supercapacitors. The high specific surface area, theoretical adjacent layers, such as alternative forms of graphene, carbon
capacitance, and excellent conductivity of these materials nanotubes, or conducting polymers [5], [10]. These spacers
enable efficient energy storage through electrical double-layer help maintain interlayer separation and enhance ion
capacitance (EDLC), making graphene an ideal candidate for accessibility. Moreover, incorporating foreign materials can
high-performance electrochemical storage systems, such as lead to the formation of hybrid structures, like those
combining MoS₂ with other materials, which can enhance interlayer separation but also introduces hierarchical porosity,
electrochemical performance due to the complementary creating additional ion transport pathways. These 2D–2D
properties of the constituents. Designing three-dimensional hybrid heterostructures significantly enhance the
porous frameworks has also proven effective in increasing ion electrochemical properties of MXenes, resulting in higher
transport pathways and maintaining high surface areas, further gravimetric capacitance, better rate capability, and improved
boosting performance [12]. Ordered mesoporous carbon cycling stability [7].
(OMC) is a type of carbon material that possesses a highly
ordered mesoporous structure, meaning it contains pores that D. Nitrogen Doping in Carbon-Based Materials
are uniform in size and well-arranged. Using OMC creates a
Nitrogen doping in carbon materials significantly
more stable, ordered mesoporous network in which the
enhances their electrochemical performance, making them
material is better able to maintain its surface area, as the
highly suitable for energy storage applications such as
carbon ‘pillars’ arranged in the mesoporous layer prevent the
supercapacitors. The introduction of nitrogen atoms into the
layers from coming together. OMC structures tend to have
carbon framework modifies the electronic structure, increases
higher electrochemical stability because the pores help
conductivity, and introduces active sites that contribute to
accommodate volume changes during charge/discharge cycles,
pseudocapacitance [15]. Pseudocapacitance is capacitance that
reducing stress on the material and preventing degradation
results not from the accumulation of an EDLC but from the
over time [7].
adsorption of electrochemical species on electrode surfaces,
C. A Carbon-Based Graphene Alternative which includes adsorption, redox, and intercalation
pseudocapacitance [16]. Pseudocapacitive sites, such as
MXenes, a class of 2D materials composed of transition dopants susceptible to reversible redox reactions with
metal carbides, nitrides, or carbonitrides, have emerged as electrolytes, enable faradaic redox reactions, which
promising alternatives to graphene in energy storage significantly boost charge storage capacity beyond the
applications. MXenes are of the chemical formula MxAyTz, capabilities of purely double-layer capacitance [17].
where M is a metal, A is a material like carbon, and T is an
end group on the perimeter of each 2D layer. Like graphene, The effect of nitrogen doping is highly dependent on the
MXenes exhibit remarkable electronic conductivity, high nitrogen atom’s position and bonding within the carbon
surface area, and mechanical strength. However, unlike structure. Nitrogen can be incorporated into several distinct
graphene, MXenes offer an additional advantage: they can bonding configurations, such as pyridinic, pyrrolic, and
store charge through both electrical double-layer capacitance quaternary nitrogen sites. Pyridinic nitrogen, for example,
and pseudocapacitance [13], [14]. This dual energy storage tends to introduce electron-deficient sites that are beneficial
mechanism enhances their performance in supercapacitors and for increasing the material's electrochemical activity, while
batteries, making them highly suitable for energy storage pyrrolic nitrogen may contribute to the formation of
applications. MXenes are typically synthesized through redox-active sites that enhance pseudocapacitive behavior.
selective etching of the A layers from the layered MAX Quaternary nitrogen, on the other hand, is often associated
phases, resulting in highly conductive, hydrophilic materials with an increase in conductivity and structural stability [17]. It
that can efficiently intercalate ions for charge storage [1]. is known that pyridinic-N and pyrrolic-N in N-graphene
provide pseudocapacitance in proton-conducting (acid)
Despite these promising characteristics, MXenes face electrolyte, which could affect the choice of electrolyte for
challenges similar to graphene, particularly restacking. This N-MDC-OMC [18]. These various nitrogen-doping sites
not only limits ion accessibility but also negatively affects the influence not only the electrochemical properties but also the
cycling stability and performance of MXenes in energy surface morphology and distribution of nitrogen dopants,
storage systems. The strong interlayer interactions hinder which can be characterized using techniques like scanning
efficient ion diffusion, a critical factor in supercapacitor tunneling microscopy (STM) and Raman spectroscopy (RS).
applications where high surface area and rapid ion transport STM, in particular, is effective for visualizing dopant
are essential for optimal performance [4], [13]. To overcome clustering or homogeneous distribution of nitrogen sites at the
these limitations, recent studies have focused on strategies to atomic level, offering critical insights into how doping impacts
prevent restacking and enhance the electrochemical the material's overall performance [19].
performance of MXenes. A promising approach involves
incorporating mesoporous carbon (OMC) layers between
MXene sheets [2]. The mesoporous carbon not only preserves
 III. Lɪᴛᴇʀᴀᴛᴜʀᴇ Rᴇᴠɪᴇᴡ/Rᴇsᴇᴀʀᴄʜ Oʙᴊᴇᴄᴛɪᴠᴇ ion diffusion, further limiting its effectiveness in energy
storage applications.
A. Hierarchical porous carbons
In contrast, MDC-OMC offers a different set of
Our primary reference for this research is the work by advantages. While its electron mobility and conductivity may
Wang et al. [7], which presents a novel approach to addressing not match those of graphene, its structure ensures high surface
the limitations of 2D nanomaterials, specifically their natural area and allows for efficient ion diffusion [7]. The
restacking tendencies, which hinder ion diffusion and limit intercalation of mesoporous carbon layers within the MDC
their effectiveness in energy storage applications. By creating structure prevents restacking and enhances the material’s
ordered mesoporous carbon (OMC) layers between layers of capacity to store charge, making it more suitable for energy
flat MXene-derived carbon (MDC), the researchers developed storage applications like supercapacitors. By offering efficient
a hierarchical porous carbon material (MDC-OMC) with pathways for ion transport and increasing the accessible
enhanced structural stability and electrochemical performance. surface area, MDC-OMC addresses the shortcomings of
This unique 2D–2D heterostructure prevents restacking, graphene in energy storage, making it a superior choice for
facilitates ion accessibility, and maintains electron applications where charge storage and cycling stability are
conductivity within an all-carbon electrode. The MDC-OMC paramount.
material demonstrated superior performance as a
supercapacitor electrode, achieving high capacitance and C. Research Proposal
excellent cycling stability [7]. These structures may be
We propose the synthesis and characterization of doped
considered similar to graphene electrodes because of their
mesoporous carbon structures (doped MDC-OMC) and
all-carbon construction, their ‘layers’, and their similarities to
potentially doped MXene-OMC structures (e.g.,
graphene observed in XRD and RS [7], [20], [21]. However,
Ti3(NyC1-y)2Tx-OMC) with the potential for use in energy
the MDC sheets that comprise the structure are not identical to
storage applications. To assess the functional similarity of
graphene sheets and are linked to other sheets via mesoporous
doped MDC-OMC structures to graphene, we will introduce
carbon layers.
graphene dopants that may improve electrical conductivity,
B. Graphene vs. MDC-OMC pseudocapacitance, and porosity to the MDC-OMC structure.
The primary focus of the research will be to introduce
Graphene and mesoporous-derived carbon (MDC-OMC) nitrogen to MDC-OMC to synthesize and characterize
represent two distinct classes of carbon-based materials, each nitrogen-doped MDC-OMC (N-MDC-OMC) for use in
with unique properties and advantages tailored to different supercapacitor electrodes. Creating MXene-OMCs and
applications. Graphene, a single layer of carbon atoms MDC-OMC structures with alternate dopants is considered a
arranged in a two-dimensional hexagonal lattice, is notable for secondary goal.
its crystallinity and long-range order, which contribute to its
remarkable electrical properties [22]. The arrangement of The benefits of N-MDC-OMC over alternatives will
carbon atoms in graphene creates a delocalized π-electron include structural stability and properties tunability leading to
system that allows for exceptionally high electron mobility enhanced capacitance and supercapacitor lifetime. As of
[8]. This property is a direct consequence of the absence of a writing this proposal, only one group (to our knowledge) has
band gap in graphene. Electrons can move through the synthesized and characterized MDC-OMC [7]. Compared to
material with minimal resistance, contributing to its excellent prior approaches, this proposal offers a novel method of
electrical conductivity, and making it an ideal candidate for creating a high-capacitance, restacking-resistant electrode
high-speed electronic applications [5], [22]. However, these structure with tunable electronic properties adjusted by level
electronic properties come at a cost for applications such as of doping. For structural stability, the restacking resistance of
energy storage. Graphene’s lack of inherent porosity limits its MDC-OMC structures is clear given the 98% capacitance
ability to store charges volumetrically. The absence of porosity retention of supercapacitors with MDC-OMC electrodes after
in graphene prevents efficient packing of ions within its 7,000 charge-discharge cycles [7]. For properties tunability,
structure, reducing its capacitance. Moreover, graphene has a the doping level of the structure can be altered to potentially
tendency to restack into multilayered structures due to strong achieve a range of properties suitable for electrochemical
van der Waals forces between layers [5]. This restacking device applications [23].
diminishes the accessible surface area for ions and impedes
 The research will be broken into a synthesis stage, a with the dissolution of MXene sheets, copolymers/unimers,
structural characterization stage, and an electrochemical and resol in ethanol solution, and (a) evaporation-induced
characterization stage. First, N-MDC-OMC structures must be self-assembly (EISA) is performed wherein gradual
synthesized with dopants. We will investigate the use of doped evaporation of the solution causes the copolymers and resol to
MXenes in MDC-OMC synthesis, wherein the dopants are self-assemble into micelles between the MXene layers; (b)
included in the MXene sheets used to synthesize MDC-OMC. thermal treatment of the MXene-micelle composite carbonizes
We believe that the MDC-OMC synthesis method employed the structure, leading to a hybrid composite of MXene layers
by Wang et al [7] will remain effective with this change, but interspersed between ordered mesoporous carbon layers; and
possible difficulties are considered. The main dopant of (c) chlorination is used to etch the metal from the MXene and
interest is nitrogen: as discussed above, nitrogen enhances the leave behind an all-carbon structure [7]. See [7] for full details
conductive properties of graphene. Nitrogen may be added to of the synthesis procedure.
the process at a plurality of dopant concentrations for tunable
N-MDC-OMC. To assess the tunability of the structure and the We propose that nitrogen-doped carbon should be
effect of doping on the structure, we propose using a plurality introduced before step (a) to the structure by substituting
of doping levels, from 0% doping (control) to 50% doping as Ti3C2Tx MXenes with Ti3(NyC1-y)2Tx MXenes with y varying
allowed by well-established MXene synthesis methods [23]. from y = 0 to y = 0.5, leading to nitrogen-doped MDC-OMC
(N-MDC-OMC). Ti3(NyC1-y)2Tx MXenes can be synthesized at
Second, the structures must be characterized to confirm a plurality of nitrogen concentrations starting with materials
the introduction of the dopant and to observe any ensuing readily available from chemical suppliers [23]. Furthermore,
alteration to the MDC-OMC structures. X-ray diffraction this method allows for the use of a variety of dopants,
(XRD) will be used to confirm the removal of metals from the allowing for the creation of a plurality of doped MDC-OMC
MXene and the OMC structure. To characterize the presence structures [25]. While a doping method employed after step
of dopants in synthesized doped MDC-OMC structures, (c) would avoid chemical reactivities during the synthesis
Raman spectroscopy (RS) will be used. Scanning tunneling process, such a method may not distribute dopants uniformly
microscopy (STM) will be used to identify structural defects throughout the structure.
such as vacancies arising from the introduction of dopants to
the all-carbon structure. Scanning electron microscopy (SEM) The stability of these MXenes during the synthesis
and tunneling electron microscopy (TEM) may also be used process may be compromised by unintended chemical
to resolve the existence of mesoporous structures and the reactivity pathways for nitrogen-in-graphene or by the
various layers expected in doped MDC-OMC. high-temperatures required for synthesis. For instance, in
Ti3(NyC1−y)2Tx, vacancies increase as y increases, which is
Third, the structures will be evaluated for their use in believed to lead to water adsorption (as would be found with
energy storage devices. We expect doped MDC-OMC to an aqueous electrolyte) and a lower decomposition
perform well as a supercapacitor with enhanced gravimetric temperature [23]. The carbonization of Ti3C2Tx and resol-F127
capacitance (>255 F/g [7]) as induced by dopants with unimers to produce Ti3C2Tx-OMC occurs at 900 °C and is
pseudocapacitive effects, and with improved cycling stability performed in a nitrogen atmosphere [7]. Notably, thermal
as compared to other graphene electrodes (>95% after 5,000 decomposition of Ti3(NyC1−y)2Tx begins at 500 °C for T = Cl
cycles [24]). Nitrogen doping in particular may introduce [23]. However, carbonization of Ti3C2Tx-OMC at 900 °C in
pseudocapacitance to the cell, increasing the overall MDC-OMC synthesis was evidently not an issue, and
capacitance. For comparing the synthesized structures to HF-etched Ti3(NyC1−y)2Tx (T = F, OH) does not decompose
literature and demonstrating the practicality of N-MDC-OMC until 800 °C in case a variant is needed with greater thermal
in electrochemical devices, a capacitor with N-MDC-OMC stability [7], [23]. Thus, it is assumed that no major changes
electrodes will be constructed using low-cost materials. are needed for the synthesis process to produce
N-MDC-OMC. As further discussed in Wang et al [7],
electrodes with MXene-OMC materials make for effective
IV. Rᴇsᴇᴀʀᴄʜ Dᴇsɪɢɴ/Mᴇᴛʜᴏᴅᴏʟᴏɢʏ supercapacitor electrodes as well, though their gravimetric
capacitance is notably inferior to all-carbon electrodes.
A. Synthesis

As illustrated in Wang et al, preparation of the final

MDC-OMC requires three major steps. The synthesis begins
B. Structural Characterization

It is critical to understand the underlying structure of any

synthesized doped MDC-OMC (d-MDC-OMC), beginning
with N-MDC-OMC. While graphene comprises carbons
arranged in a hexagonal fashion, the N-MDC-OMC with
dopant impurities may harbor a significant amount of defects
and may possess a crystal structure distinct from graphene.
However, it remains to be seen what effect nitrogen or another
dopant would have on the structure of MDC-OMC. For
reference, the characterization of nitrogen-doped graphene
(N-graphene) is considered. Informative characterization of
N-graphene methods include X-ray photoelectron
spectroscopy (XPS), Raman spectroscopy (RS), and Scanning
Tunneling Microscopy (STM) [19], [26]. Other
characterization techniques include Atomic Force Microscopy
(AFM), angle-resolved photoelectron spectroscopy, scanning
electron microscopy (SEM), and thermogravimetric analysis
(TGA) [19]. From these, RS and STM are foreseen as most
useful when combined with X-ray diffraction.

X-ray diffraction (XRD) will first and foremost confirm

the synthesis of an MDC-OMC structure or similar. As
outlined in Wang et al, broad reflection peaks are
characteristic of disordered carbon [26]. Comparing the XRD
patterns of graphite, graphene oxide (GO), and graphene, FIG 1: XRD patterns of G/GO/G (a) [20]; MDC/mxenes (b)
MDC-OMC spectra are most similar to those of graphene, as [7]. The similar shapes of graphene in 1a and MDC-OMC in
seen in figures 1a and 1b. [20]. However, in the event of 1b are indicative to the structure of MDC-OMC as more akin
chemical breakdown due to the presence of any dopant, to graphene than other carbon allotropes.
graphite or graphene oxide may be present. Their peaks on an
XRD plot would clearly indicate an unsuccessful synthesis of Raman spectroscopy (RS) is considered the most relevant
d-MDC-OMC. materials characterization method owing to its use in
characterizing graphene, graphitic carbon, and MXenes. RS
For nitrogen as a dopant, XRD will not be useful for measures light that is not scattered elastically, including
determining the final nitrogen content of N-MDC-OMC Stokes and Anti-Stokes scattering wherein a lower-energy
structures. The spectra reported in the Ti3(NyC1-y)2Tx MXenes photon is emitted when energy is absorbed or a higher-energy
synthesized by Zhang et al show no significant difference photon is emitted after further energizing a pre-excited state
between samples as nitrogen content is varied [23]. Moreover, [27]. Solids absorb this additional energy as phonons, as
XRD may also show impurities from the MXene sample: the demonstrated when the 2D and D bands on N-graphene
differing XRD results of Wang and Zhang may be attributed to Raman spectra occur as energy is absorbed by zone-boundary
the different terminal groups present on the MXenes used in phonons [21], [27].
each study (T = -OH and -F versus T = -Cl) [23], [26]. While
Zhang et al outlines the dependence of the a-lattice parameter Similar Raman spectra of N-MDC-OMC to those
in the Ti3(NyC1-y)2Tx MXene on nitrogen content – an produced for N-graphene may be indicative of nitrogen
important solid-state characteristic descriptive of the crystal content within N-MDC-OMC samples. If the structures are
structure – it will be necessary to distinguish nitrogen within dissimilar in RS but similar in XRD, characteristics of the new
the all-carbon structure [23]. structures can be determined by analyzing the Raman spectra
to determine vibrational modes of the N-MDC-OMC. In RS
studies of N-graphene, peaks typically appear around
1320–1350 (the D peak), 1570–1585 (the G peak), and
2640–2680 (the 2D peak) 1/cm [21]. The D and 2D peaks
correspond to disordered carbon while the G peaks correspond favored along grain boundaries/edges) of different types of
to graphitic carbon; for comparison, the spectra of MDC-OMC nitrogen doping that may occur in the sample (pyridinic,
is provided [26]. The ratio of ID/IG characterizes the level of pyrrolic, and quaternary), and can demonstrate phenomena
disorder in graphene, as discussed further in [21], and such as dopant clustering [19]. Presumably, a random spread
N-graphene is expected to have a more pronounced D peak of dopants is desired to homogenize the properties of any
with broadened D and G peaks as compared to pristine device using doped MDC-OMC. As the charge-carrier density
graphene [19]. (n = ED2/π(h̅vF)2 (where n is the charge-carrier density, ED is
the energy at the Dirac point, h̅ is the reduced Planck constant,
and νF is the Fermi velocity) of N-graphene may be measured
from STM, it may also be measured for N-doped MDC-OMC
[19].

Supplementary methods will include scanning electron

microscopy (SEM) and transmission electron microscopy
(TEM) studies. SEM and TEM will be useful in identifying
the long-range morphology of the N-MDC-OMC structure.
Particularly, the SEM morphology of each structure depending
on nitrogen content can be compared to one another to see if
nitrogen affects the mesoporosity of the structure. We would
expect minimal effects at minimal dopant concentration.

C. Electrochemical characterization

To evaluate the practical usage of N-MDC-OMC,

laboratory-scale supercapacitors with N-MDC-OMC
electrodes will be tested. The nitrogen doping is expected to
introduce pseudocapacitance to the material and thus increase
gravimetric capacitance.

To construct electrodes, N-MDC-OMC films will be

placed on a conductor like aluminum foil then placed opposite
another electrode, as per typical construction procedure of
graphene electrodes and the construction used for MDC-OMC
electrodes [5], [26]. Apart from the N-MDC-OMC itself, low
cost materials are preferred, including aluminum for the
FIG 2: Irradiated graphene Raman spectrum (a) [7].
conductors and aqueous potassium hydroxide (KOH) for the
MDC-OMC Raman spectrum (b) [18]. Wang et al did not
electrolyte. While acidic solution is preferred for enabling
report the Raman shift above 2400 cm-1 as necessary for a
pseudocapacitance with nitrogen dopants in the form of
direct comparison.
hydrogen-nitrogen redox couples, KOH will also be used to
It is hoped that characterizing the N-MDC-OMC structure compare N-MDC-OMC directly to experiments from the
with RS will shed light on the similarity of N-MDC-OMC to literature.
N-graphene and a difference between MDC-OMC and
The N-MDC-OMC supercapacitors will be evaluated
N-MDC-OMC. An N-MDC-OMC structure akin to
using electrochemical impedance spectroscopy (EIS) and
N-graphene will likely have the properties of N-graphene
cycle life tests. In EIS, the response of an electrochemical
without the issue of restacking as mitigated by the
system to an applied sinusoidal current or voltage is measured.
aforementioned synthesis method. However, RS may not
For instance, in cyclic voltammetry, the voltage (V) applied to
resolve atomic-level defects and surface phenomena of
a system is altered according to a scan rate (typically mV/s)
N-MDC-OMC. We propose scanning tunneling microscopy
set to a particular frequency. The output current of the
(STM) characterization to characterize the surface and defect
electrochemical system then characterizes the system at a
behavior of N-MDC-OMC. The images produced by STM
particular scan rate [28]. Gravimetric capacitance, volumetric
will provide insight to the frequency and distribution (i.e.,
capacitance, energy density, and power density are the target 5,000 cycles, C-NGNS-900s retained 96.1% capacitance and
performance metrics expected to be exceeded as compared C-NGNS-750s retained 93.7% of capacitance compared to
with other carbon-based electrodes and as compared to <90% stability for all-carbon non-crumpled graphene
non-doped MDC-OMC electrodes. Wang et al provides a few supercapacitors [24]. Wang et al tested MDC-OMC to 7,000
examples for comparison as shown in Table 2; data for a cycles and found that the electrodes retained 98% capacitance
nitrogen-doped graphene electrode from Wen et al is also [26]. N-MDC-OMC electrodes will be tested to at least 104
included [7], [24]. cycles, and if a similar stability to MDC-OMC is achieved, the
electrode will be tested to 105 cycles.
Material Scan Gravimetric Volumetric Electrolyte
rate/ capacitance capacitance
current (F/g) (F/cm3) V. Pʀᴇʟɪᴍɪɴᴀʀʏ Iᴍᴘʟɪᴄᴀᴛɪᴏɴs
density

The anticipated findings from this research are expected

Commercial N/A 160-200 80-110 6M KOH
activated
to significantly advance the fields of materials science and
carbon electrochemistry by providing the scientific community with
an understanding of nitrogen-doped mesoporous carbon
MDC 1 A/g 222 N/A 6M KOH structures (MDC-OMC) for energy storage applications.
Through the integration of nitrogen doping, this research will
C-NGNS-900 1.0 A/g 245.9 N/A 1.0 M explore how dopants and dopant distribution influence key
[Bu4N]BF4 material properties such as conductivity, charge-carrier
density, surface area, and mechanical stability. Structural
Ti3C2Tx-OMC 0.5 A/g 67 208 6 M KOH
characterization techniques, including Raman spectroscopy,
X-ray diffraction, and electron microscopy will elucidate the
MDC-OMC 0.5 A/g 255 212 6 M KOH
interactions between nitrogen dopants and mesoporous
architectures, which together are expected to provide
Table 2: capacitance characteristics of carbon-based pseudocapacitance and improve cycle stability. These insights
electrodes. [24], [26] are expected to address persistent challenges like material
restacking and degradation in supercapacitor electrodes and
Using the output current I, the gravimetric capacitance is
𝐼∆𝑡 lower-than-theoretical capacitance values, paving the way for
calculated with 𝐶𝑚 = 𝑚∆𝑉
for a current I, discharge time delta more stable, high-performance materials.
t, mass of active material m, and voltage range delta V [26].
The volumetric capacitance is the gravimetric capacitance By shifting the focus from traditional graphitic carbons
multiplied by the density of the capacitor. The time constant of to hybrid mesoporous architectures, this work could redefine
the capacitor, which is expected to be on the orders of seconds, the role of doped carbon materials in energy storage.
is calculated as τ = 𝑅𝐶 [7]. Furthermore, the energy density Additionally, the demonstration of effective nitrogen doping
of the device will be calculated. For a capacitor, the energy may inspire future studies on alternative dopants, such as
1 2 boron or sulfur, broadening the possibilities for tailoring
density may be given as 𝐸 = 𝐶𝑉 where V is the applied
2 material properties. These findings are anticipated to bring 2D
𝐸
voltage [7]. Power density may then be calculated as 𝑃 = 𝑡
material-based supercapacitors closer to practical
for a discharge time t [7]. implementations in the renewable energy and automotive
sectors, which aligns with the growing demand for sustainable
Cycle life tests will also be carried out on N-MDC-OMC and efficient energy storage technologies.
supercapacitors. In these tests, the capacitor is charged and
discharged many times at a fixed current density [7], [24].
While an improvement in the above properties is expected due VI. Cᴏɴᴄʟᴜsɪᴏɴ
to pseudocapacitive effects of nitrogen dopants, it is known
that pseudocapacitive materials have poor cycling stability [5]. This proposal aims to create practical supercapacitor
However, Wen et al observed high stability of crumpled electrodes derived from 2D materials in the form of
nitrogen-doped graphene nanosheets (C-NGNS, with N-MDC-OMC. 2D materials possess high surface area and
following numbers indicating doping level), wherein after ideal electronic properties for supercapacitors due to nanoscale
interactions arising from their unique 2D structure.
MXene-derived carbon will be doped with nitrogen for
increased capacitance compared to all-carbon MDC-OMC,
and the MDC-OMC structure is expected to provide high
resistance to restacking and long-term supercapacitor stability.
Overall, we expect this to lead to a supercapacitor with a
gravimetric capacitance exceeding 250 F/g and a >95%
capacitance retention after 5,000 cycles as compared to
previous research into MDC-OMC and nitrogen-doped
graphene electrodes. These properties will make 2D-derived
materials more attractive for usage in the transport and
renewable energy sectors, accelerating the global transition to
net-zero carbon emissions.
 VII. RᴇFᴇʀᴇɴᴄᴇs 24, pp. 22–51, Jan. 2020, doi: 10.1016/j.ensm.2019.08.004.
[15] C. Lu et al., “Nitrogen‐Doped Ti3 C2 MXene: Mechanism
Investigation and Electrochemical Analysis,” Adv. Funct.
[1] O. US EPA, “Sources of Greenhouse Gas Emissions.”
Mater., vol. 30, no. 47, p. 2000852, Nov. 2020, doi:
Accessed: Dec. 04, 2024. [Online]. Available:
10.1002/adfm.202000852.
https://www.epa.gov/ghgemissions/sources-greenhouse-gas-emi
[16] S. Fleischmann et al., “Pseudocapacitance: From Fundamental
ssions
Understanding to High Power Energy Storage Materials,”
[2] H. Ritchie, “The end of range anxiety: how has the range of
Chem. Rev., vol. 120, no. 14, pp. 6738–6782, Jul. 2020, doi:
electric cars changed over time?” Accessed: Dec. 06, 2024.
10.1021/acs.chemrev.0c00170.
[Online]. Available:
[17] Y. Deng, Y. Xie, K. Zou, and X. Ji, “Review on recent advances
https://www.sustainabilitybynumbers.com/p/electric-car-range
in nitrogen-doped carbons: preparations and applications in
[3] “Confronting the Duck Curve: How to Address
supercapacitors,” J. Mater. Chem. A, vol. 4, no. 4, pp.
Over-Generation of Solar Energy,” Energy.gov. Accessed: Dec.
1144–1173, 2016, doi: 10.1039/C5TA08620E.
06, 2024. [Online]. Available:
[18] Y.-H. Lee, K.-H. Chang, and C.-C. Hu, “Differentiate the
https://www.energy.gov/eere/articles/confronting-duck-curve-ho
pseudocapacitance and double-layer capacitance contributions
w-address-over-generation-solar-energy
for nitrogen-doped reduced graphene oxide in acidic and
[4] J. Zhang, M. Gu, and X. Chen, “Supercapacitors for renewable
alkaline electrolytes,” J. Power Sources, vol. 227, pp. 300–308,
energy applications: A review,” Micro Nano Eng., vol. 21, p.
Apr. 2013, doi: 10.1016/j.jpowsour.2012.11.026.
100229, Dec. 2023, doi: 10.1016/j.mne.2023.100229.
[19] H. Wang, T. Maiyalagan, and X. Wang, “Review on Recent
[5] J. Li and M. Östling, “Prevention of Graphene Restacking for
Progress in Nitrogen-Doped Graphene: Synthesis,
Performance Boost of Supercapacitors—A Review,” Crystals,
Characterization, and Its Potential Applications,” ACS Catal.,
vol. 3, no. 1, pp. 163–190, Mar. 2013, doi:
vol. 2, no. 5, pp. 781–794, May 2012, doi: 10.1021/cs200652y.
10.3390/cryst3010163.
[20] F. T. Johra, J.-W. Lee, and W.-G. Jung, “Facile and safe
[6] J. Wang, V. Malgras, Y. Sugahara, and Y. Yamauchi,
graphene preparation on solution based platform,” J. Ind. Eng.
“Electrochemical energy storage performance of 2D
Chem., vol. 20, no. 5, pp. 2883–2887, Sep. 2014, doi:
nanoarchitectured hybrid materials,” Nat. Commun., vol. 12, no.
10.1016/j.jiec.2013.11.022.
1, p. 3563, Jun. 2021, doi: 10.1038/s41467-021-23819-0.
[21] I. Childres, L. A. Jauregui, W. Park, H. Cao, and Y. P. Chen,
[7] J. Wang et al., “Hierarchical porous carbons with layer-by-layer
“RAMAN SPECTROSCOPY OF GRAPHENE AND
motif architectures from confined soft-template self-assembly in
RELATED MATERIALS”.
layered materials,” Nat. Commun., vol. 8, no. 1, p. 15717, Jun.
[22] A. R. Urade, I. Lahiri, and K. S. Suresh, “Graphene Properties,
2017, doi: 10.1038/ncomms15717.
Synthesis and Applications: A Review,” JOM, vol. 75, no. 3,
[8] Q. Abbas et al., “Graphene Synthesis Techniques and
pp. 614–630, Mar. 2023, doi: 10.1007/s11837-022-05505-8.
Environmental Applications,” Materials, vol. 15, no. 21, p.
[23] T. Zhang, C. E. Shuck, K. Shevchuk, M. Anayee, and Y.
7804, Nov. 2022, doi: 10.3390/ma15217804.
Gogotsi, “Synthesis of Three Families of Titanium Carbonitride
[9] K. S. Novoselov et al., “Two-dimensional gas of massless Dirac
MXenes,” J. Am. Chem. Soc., vol. 145, no. 41, pp.
fermions in graphene,” Nature, vol. 438, no. 7065, Art. no.
22374–22383, Oct. 2023, doi: 10.1021/jacs.3c04712.
7065, Nov. 2005, doi: 10.1038/nature04233.
[24] Z. Wen et al., “Crumpled Nitrogen‐Doped Graphene
[10] A. Bouzina, H. Perrot, O. Sel, and C. Debiemme-Chouvy,
Nanosheets with Ultrahigh Pore Volume for High‐Performance
“Preventing Graphene from Restacking via Bioinspired
Supercapacitor,” Adv. Mater., vol. 24, no. 41, pp. 5610–5616,
Chemical Inserts: Toward a Superior 2D Micro-supercapacitor
Nov. 2012, doi: 10.1002/adma.201201920.
Electrode,” ACS Appl. Nano Mater., vol. 4, no. 5, pp.
[25] R. Wang, M. Li, K. Sun, Y. Zhang, J. Li, and W. Bao,
4964–4973, May 2021, doi: 10.1021/acsanm.1c00489.
“Element‐Doped Mxenes: Mechanism, Synthesis, and
[11] D. P. Chatterjee and A. K. Nandi, “A review on the recent
Applications,” Small, vol. 18, no. 25, p. 2201740, Jun. 2022,
advances in hybrid supercapacitors,” J. Mater. Chem. A, vol. 9,
doi: 10.1002/smll.202201740.
no. 29, pp. 15880–15918, 2021, doi: 10.1039/D1TA02505H.
[27] L. A. K. Staveley, The Characterization of Chemical Purity:
[12] Y. Han, Y. Ge, Y. Chao, C. Wang, and G. G. Wallace, “Recent
Organic Compounds. Butterworth-Heinemann. Accessed: Dec.
progress in 2D materials for flexible supercapacitors,” J. Energy
03, 2024. [Online]. Available:
Chem., vol. 27, no. 1, pp. 57–72, Jan. 2018, doi:
https://www.sciencedirect.com/book/9780408701457/the-charac
10.1016/j.jechem.2017.10.033.
terization-of-chemical-purity
[13] N. Ahmad et al., “2D MXenes and their composites; design,
[28] N. Elgrishi, K. J. Rountree, B. D. McCarthy, E. S. Rountree, T.
synthesis, and environmental sensing applications,”
T. Eisenhart, and J. L. Dempsey, “A Practical Beginner’s Guide
Chemosphere, vol. 352, p. 141280, Mar. 2024, doi:
to Cyclic Voltammetry,” J. Chem. Educ., vol. 95, no. 2, pp.
10.1016/j.chemosphere.2024.141280.
197–206, Feb. 2018, doi: 10.1021/acs.jchemed.7b00361.
[14] B. Wang et al., “Graphene-based composites for
electrochemical energy storage,” Energy Storage Mater., vol.