NITROGEN ENRICHED CARBON DERIVED FROM ALBIZIA PROCERA LEAVES

Abstract

A method of preparing porous nitrogen-doped carbon nanosheets by pyrolysis of Albizia procera leaves. The nitrogen-doped carbon nanosheets display enhanced electrochemical properties including large surface area and specific capacitance. Electrodes coated with the nitrogen-doped carbon nanosheets are particularly suitable for use in supercapacitors and solar cells.

Claims

1: A method of preparing nitrogen doped carbon nanosheets, comprising: mixing dried and pulverized Albizia procera leaves with an activator in a mass ratio in the range of 0.1-1.0 to form a mixture, and heating the mixture in an inert atmosphere at a temperature in the range 700-1,000 C. for 2-8 hours to form the nitrogen doped carbon nanosheets.

2: The method of claim 1, wherein the activator is at least one selected from the group consisting of carbon dioxide, an alkali metal hydroxide, a metal salt, and a mineral acid.

3: The method of claim 1, wherein the activator is at least one selected from the group consisting of potassium bicarbonate, sodium bicarbonate, potassium carbonate, sodium carbonate, zinc chloride, and calcium chloride.

4: The method of claim 1, wherein the activator is potassium bicarbonate or sodium bicarbonate.

5: The method of claim 4, wherein the weight ratio of pulverized Albizia procera leaves to the activator is in the range of 0.2-0.8.

6: The method of claim 1, wherein the temperature is in the range of 800-900 C.

7: The method of claim 1, wherein the inert atmosphere is nitrogen or argon.

8: Porous nitrogen doped carbon nanosheets obtained by the method of claim 1 having a BET surface area in the range of 300-1,500 m.sup.2/g.

9: The porous nitrogen doped carbon nanosheets of claim 8 having an average pore diameter in the range of 10-50 .

10: A modified electrically conductive substrate coated with the nitrogen doped carbon nanosheets of claim 8.

11: The modified electrically conductive substrate of claim 10, wherein the carbon nanosheets are present on the surface of the substrate in an amount in the range of 0.2-10 mg/cm.sup.2.

12: The modified electrically conductive substrate of claim 10, having a specific capacitance in the range of 175-300 F/g at an applied current density of 1 A/g in 1 M sulfuric acid electrolyte.

13: The modified electrically conductive substrate of claim 10, wherein the electrically conductive substrate is glassy carbon, graphite, gold, platinum, silver, iron, copper, aluminum, or an electrically conductive polymer.

14: The modified electrode of claim 13, wherein the electrically substrate is an electrically conductive polymer selected from the group consisting of a poly(p-phenylene vinylene), a poly(3-alkylthiophene), a polyacetylene, a poly(fluorine), a polypyrene, a polyazulene, a polynaphthalene, a polypyrole, a polyaniline, a polycarbazole, a polyazepine, a polyindole, a polythiophene, a poly(3,4-ethylenedioxythiophene), and a poly(p-phenylene sulfide).

15: A method of making the modified electrically conductive substrate of claim 10 comprising: preparing a slurry of the porous nitrogen doped carbon nanosheets in a solvent containing tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer (Nafion) in an amount in the range of 0.001 wt. % to 0.01 wt. %, sonicating the slurry to form a suspension, depositing the suspension on the surface of an electrically conductive substrate, drying the deposited suspension on the electrically conductive substrate surface, and repeating the depositing and drying steps until a catalyst loading of 0.2-10 mg/cm.sup.2.

16: The method of claim 15, wherein the electrically conductive substrate is glassy carbon, graphite, gold, platinum, silver, iron, copper, aluminum or an electrically conductive polymer.

17: The modified electrode of claim 16, wherein the electrically substrate is an electrically conductive polymer selected from the group consisting of a poly(p-phenylene vinylene), a poly(3-alkylthiophene), a polyacetylene, a poly(fluorine), a polypyrene, a polyazulene, a polynaphthalene, a polypyrole, a polyaniline, a polycarbazole, a polyazepine, a polyindole, a polythiophene, a poly(3,4-ethylenedioxythiophene), and a poly(p-phenylene sulfide).

18: An electrochemical cell comprising at least one electrode which is the modified electrically conductive substrate of claim 10.

19: The electrochemical cell of claim 18, wherein the electrolyte is an aqueous alkali metal hydroxide or a mineral acid at a concentration in the range of 0.1 to 2.0 M.

20: A supercapacitor comprising at least one electrode which is the modified electrically conductive substrate of claim 10.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0045] A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:

[0046] FIG. 1 shows Scheme I for the preparation of carbon samples from Albizia procera tree leaves.

[0047] FIG. 2 shows a graph illustrating the nitrogen isothermal analysis WANC, ZnNC, and NaNC activated carbon samples.

[0048] FIG. 3 shows Raman spectra of WANC, ZnNC and NaNC activated carbon samples.

[0049] FIG. 4 shows X-ray diffraction patterns of WANC, ZnNC, and NaNC activated carbon samples.

[0050] FIG. 5A shows a SEM image of WANC activated carbon.

[0051] FIG. 5B shows a TEM image of WANC activated carbon.

[0052] FIG. 5C shows a SEM image of ZnNC activated carbon.

[0053] FIG. 5D shows a TEM image of ZnNC activated carbon.

[0054] FIG. 5E shows a SEM image of NaNC activated carbon.

[0055] FIG. 5F shows a TEM image of NaNC activated carbon.

[0056] FIG. 6A shows X-ray photoelectron spectra (XPS) of NaNC.

[0057] FIG. 6B shows XPS of NaNC (C is) deconvoluted.

[0058] FIG. 6C shows XPS of NaNC (O is) deconvoluted.

[0059] FIG. 6D shows XPS of NaNC (N Is) deconvoluted.

[0060] FIG. 7 shows Fourier transform infrared spectra of: (a) WANC (b) ZnNC and (c) NaNC activated carbons.

[0061] FIG. 8A shows CV curves obtained at scanning rate of 20 mV/s of electrodes coated with WANC, ZnNC, and NaNC.

[0062] FIG. 8B shows GCD curves obtained at current density of 2 A/g of an electrode coated with WANC, ZnNC, and NaNC.

[0063] FIG. 9A shows CV curves for NaNC electrode at scan rates of 5, 10, 20, and 50 mV s.sup.1.

[0064] FIG. 9B shows GCD curves at current densities of 1, 2, 5, and 10 A/g of an electrode coated with NaNC.

[0065] FIG. 9C shows 20 GCD cycles of NaNC activated carbon electrode at current densities of 20 A/g.

[0066] FIG. 9D shows capacitance retention of NaNC activated carbon electrode at current densities of 20 A/g.

DETAILED DESCRIPTION

[0067] Embodiments of the present disclosure will now be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the disclosure are shown. The present disclosure will be better understood with reference to the following definitions.

[0068] All publications mentioned herein are incorporated herein by reference in full for the purpose of describing and disclosing the methodologies, which are described in the publications, which might be used in connection with the description herein. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior disclosure. Also, the use of or means and/or unless stated otherwise. Similarly, comprise, comprises, comprising include, includes, and including are interchangeable and not intended to be limiting.

[0069] Unless otherwise specified, a or an means one or more.

[0070] Terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0071] The headings (such as Background and Summary) and sub-headings used herein are intended only for general organization of topics within the present invention, and are not intended to limit the disclosure of the present invention or any aspect thereof. In particular, subject matter disclosed in the Background may include novel technology and may not constitute a recitation of prior art. Subject matter disclosed in the Summary is not an exhaustive or complete disclosure of the entire scope of the technology or any embodiments thereof. Classification or discussion of a material within a section of this specification as having a particular utility is made for convenience, and no inference should be drawn that the material must necessarily or solely function in accordance with its classification herein when it is used in any given composition.

[0072] It will be further understood that the terms comprises and/or comprising, when used in this specification, specify the presence of stated features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof.

[0073] As used herein, the term and/or includes any and all combinations of one or more of the associated listed items.

[0074] As used herein in the specification and claims, including as used in the examples and unless otherwise expressly specified, all numbers may be read as if prefaced by the word substantially, about or approximately, even if the term does not expressly appear. As used herein, the term about refers to an approximate number within 20% of a stated value, preferably within 15% of a stated value, more preferably within 10% of a stated value, and most preferably within 5% of a stated value. For example, if a stated value is about 8.0, the value may vary in the range of 81.6, 1.0, 0.8, 0.5, 0.4, 0.3, 0.2, or 0.1.

[0075] Disclosure of values and ranges of values for specific parameters (such as temperatures, molecular weights, weight percentages, etc.) are not exclusive of other values and ranges of values useful herein. It is envisioned that two or more specific exemplified values for a given parameter may define endpoints for a range of values that may be claimed for the parameter. For example, if Parameter X is exemplified herein to have value A and also exemplified to have value Z, it is envisioned that parameter X may have a range of values from about A to about Z. Similarly, it is envisioned that disclosure of two or more ranges of values for a parameter (whether such ranges are nested, overlapping or distinct) subsume all possible combination of ranges for the value that might be claimed using endpoints of the disclosed ranges. For example, if parameter X is exemplified herein to have values in the range of 1-10 it also describes subranges for Parameter X including 1-9, 1-8, 1-7, 2-9, 2-8, 2-7, 3-9, 3-8, 3-7, 2-8, 3-7, 4-6, or 7-10, 8-10 or 9-10 as mere examples. A range encompasses its endpoints as well as values inside of an endpoint, for example, the range 0-5 includes 0, >0, 1, 2, 3, 4, <5 and 5.

[0076] As used herein, the words preferred and preferably refer to embodiments of the technology that afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the technology.

[0077] As referred to herein, all compositional percentages are by weight of the total composition, unless otherwise specified. As used herein, the word include, and its variants, is intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that may also be useful in the materials, compositions, devices, and methods of this technology. Similarly, the terms can and may and their variants are intended to be non-limiting, such that recitation that an embodiment can or may comprise certain elements or features does not exclude other embodiments of the present invention that do not contain those elements or features.

[0078] The description and specific examples, while indicating embodiments of the technology, are intended for purposes of illustration only and are not intended to limit the scope of the technology. Moreover, recitation of multiple embodiments having stated features is not intended to exclude other embodiments having additional features, or other embodiments incorporating different combinations of the stated features. Specific examples are provided for illustrative purposes of how to make and use the compositions and methods of this technology and, unless explicitly stated otherwise, are not intended to be a representation that given embodiments of this technology have, or have not, been made or tested.

[0079] According to a first aspect, the present disclosure relates to a method of preparing nitrogen doped carbon nanosheets comprises mixing dried and pulverized plant materials with an activator, and heating the mixture in an inert atmosphere at a temperature in the range of 600-1,200 C., preferably in the range of 700-1,000 C., preferably in the range of 750-950 C., preferably about 850 C. for a time in the range of 1-10 hours, preferably 2-8 hours, preferably 4-6 hours, and preferably about 5 hours. The plant materials may be leaves, branches, wood, flowers, fruits, seeds, husks, strew, roots, and the like.

[0080] In some embodiments, the plant material is from the genus Albizia, which is a genus of more than 160 species of mostly fast-growing subtropical and tropical trees and shrubs in the subfamily Mimosoideae of the family Fabaceae. The genus is pantropical, occurring in Asia, Africa, Madagascar, America and Australia, but mostly in the Old World tropics. In some locations, some species are considered weeds. They are commonly called silk plants, silk trees, or sirises. In some preferred embodiments, the Albizia species is Albizia procera, commonly known as white siris. In a particularly preferred embodiment, the plant material is leaves from Albizia procera.

[0081] In general, the plant material is washed with water and air dried for a time in the range of 12-144 hours, preferably 18-120 hours, preferably 24-96 hours, preferably 36-65, preferably 40-55 hours, preferably about 48 hours. In some embodiments, the air drying time may be more than 144 hours or less than 12 hours depending on the air temperature and humidity. The air dried leaves are further oven dried at a temperature in the range of 70-130 C., preferably 80-120 C., preferably 90-110 C., preferably about 100 C. for a time in the range of 12-144 hours, preferably 18-120 hours, preferably 24-96 hours, preferably 36-65, preferably 40-55 hours, preferably about 48 hours, preferably in the presence of a dessicant. The oven dried leaves are pulverized by any tools available such as but not limited to mortar and pestle, and a homogenizer including kitchen or laboratory blender may be used to grind the dried leaves to obtain a plant material dry fine powder.

[0082] To obtain the nitrogen doped carbon nanosheets, the plant material dry fine powder (FP) is mixed with an activator (A) in FP/A ratio in the range of 0.10-1.00, preferably 0.20-0.80, preferably 0.25-0.60, preferably 0.33. Any activator may be utilized in the method of the invention such as, but not limited to carbon dioxide, a metal salt, an alkali or alkaline earth metal hydroxide, and a mineral acid. Examples of metal salts include, but are not limited to sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and calcium or zinc halide such as calcium chloride, zinc chloride, zinc bromide, calcium iodide, zinc fluoride, and the like. Examples of alkali or alkaline earth metal hydroxides include, but are not limited to potassium hydroxide, sodium hydroxide, calcium hydroxide, and the like. Examples of mineral acids include, but are not limited to, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, and the like. The mixture of the plant material dry fine powder and the activator is heated under inert gas such as, but not limited to nitrogen, helium, and argon. The resulting activated carbon may be washed with mineral acid such as but not limited to hydrochloric acid at a concentration in the range of 0.1-2.0 M, preferably 0.5-1.5 M, preferably about 1.0 and deionized water. The washed activated carbon is dried at a temperature in in the range of 50-90 C., preferably 55-75 C., preferably 60-70 C., preferably about 60 C. for a time in the range of 10-96 hours, preferably 15-72 hours, preferably 20-36 hours, preferably about 24 hours.

[0083] Another aspect of the invention is directed to a porous nitrogen doped carbon nanoparticles obtained by the method described herein. The size and morphology of the nitrogen doped carbon particles may vary depending on the plant material used, the activator used, and the heating temperature. The nitrogen doped carbon particles may be macroparticles, microparticles, nanoparticles, or combination thereof, having any morphology. Examples of the morphology of the activated carbon nanoparticles include but are not limited to nanosheets, nanospheres, hollow nanospheres, nanorods, and hollow nanorods. In some embodiments, the activated nitrogen doped carbon nanoparticles are nanosheets having a diameter in the range of 10-999 nm, preferably 20-600 nm, preferably 40-400 nm, preferably 60-200 nm. The nitrogen doped activated carbon nanosheets of the invention are highly porous with a BET surface area in the range of 300-2,500 m.sup.2/g, preferably 500-2,000 m.sup.2/g, preferably 700-1,500 m.sup.2/g, preferably 800-1,000 m.sup.2/g, preferably 850-950 m.sup.2/g. The pore size of the nitrogen doped carbon nanosheets may vary greatly depending on the plant material and the activator used as well as the temperature of the activation and the particle size of powder precursor used. The nitrogen doped carbon nanosheets may have micropores, mesopores, macropores or combinations thereof. In some embodiments, the average pore diameter is in the range of 1-80 , preferably 5-60 , preferably 10-50 , preferably 15-40 , preferably 20-30 , preferably about 28 .

[0084] Another aspect of the invention is directed to a modified electrically conductive substrate coated with the nitrogen doped carbon nanosheets of the invention. The substrate is any electrically conductive material. Examples of electrically conductive metals include but not limited to graphite, graphene, copper, aluminum, iron, silver, gold, lead, and zinc. Other conductive substrate includes organic polymers wherein the main polymer chain contains one or more of an aromatic ring, double bond, and combination of aromatic ring and double bond. Examples of conductive polymers include but are not limited to a poly(p-phenylene vinylene), a poly(3-alkylthiophene), a polyacetylene, a poly(fluorine), a polypyrene, a polyazulene, a polynaphthalene, a polypyrol, a polyaniline, a polycarbazole, a polyazepine, a polypyrole, a polyindole, a polythiophene, a poly(3,4-ethylenedioxythiophene), and a poly(p-phenylene sulfide). In some embodiments, the substrate is a polythiophene in the form of a white solid having the chemical formula (C.sub.4H.sub.2S).sub.n. The thiophene rings are linked through the 2- and 5-positions. Substituted poly(alkylthiophene) at the 3- or 4-position tend to be soluble in organic solvents. Polythiophenes become conductive when oxidized. A variety of oxidizing reagents have been used to dope polythiophenes. Iodine and bromine produce highly conductive materials, which are unstable due to slow evaporation of the halogen. Organic acids such as, but not limited to trifluoroacetic acid, propionic acid, and sulfonic acids produce polythiophenes with lower conductivities than iodine, but the resulting polymer has higher environmental stabilities. Oxidative polymerization of thiophenes catalyzed by ferric chloride can result in a polymer doped with the catalyst. Poly(3-octylthiophene) dissolved in toluene can be doped by solutions of ferric chloride hexahydrate dissolved in acetonitrile, and can be cast into films with conductivities reaching 1 S/cm. Other, less common dopants include gold trichloride and trifluoromethanesulfonic acid. The electrical conductivity polythiophenes results from the delocalization of electrons along the polymer backbone. Polythiophenes substrates coated with the carbon nanosheets of the invention are particularly suitable for use in batteries, solar panels, and supercapacitors.

[0085] The substrate may have any dimension and shape. For example, the shape of substrate may be a cylindrical rod, a plate, a rectangular sheet, or a block. In some embodiments, the substrate is cylindrical and has a diameter at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mm and a surface area of at least 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50 Cm.sup.2. In some other embodiments, the substrate is a rectangular sheet of any length and width suitable for use in any application, in particular, for use in supercapacitor. The substrate is modified by coating with a composition comprising the nitrogen doped carbon nanosheets of the invention with a carbon nanosheet loading in the range of 0.1-15 mg/cm.sup.2, preferably in the range of 0.2-10 mg/cm.sup.2, preferably in the range of 0.3-5 mg/cm.sup.2, preferably in the range of 0.5-2 mg/cm.sup.2, and preferably about 1.0 mg/cm.sup.2 of the surface of the electrode.

[0086] In some embodiments, the BET surface area of the modified substrate is in the range of 300-2,500 m.sup.2/g, preferably 500-2,000 m.sup.2/g, preferably 700-1,500 m.sup.2/g, preferably 800-1,000 m.sup.2/g, preferably 850-950 m.sup.2/g, preferably about 910 m.sup.2/g.

[0087] In addition to the large electroactive surface area, the modified substrate of the invention has many desirable characteristics that enhance its performance as an electrode in an electrochemical cell or supercapacitor. In some embodiments, the modified electrically conductive substrate of the invention has a specific capacitance in the range of 100-400 F/g, preferably 150-350 F/g, preferably 175-300 F/g, preferably 200-275 F/g, preferably 220-250 F/g, preferably about 231 at an applied current density of 1 A/g in 1 M sulfuric acid electrolyte.

[0088] Any electrically conductive substrate may be modified to produce the electrically conductive substrate of the invention. Generally the substrate is modified by a coating comprising the nitrogen doped carbon of the present invention and a binder. The nitrogen doped carbon of the invention and a binder may be wet blended in the presence of a suitable solvent or dry blended using a mortar or other conventionally known mixing equipment. The mixture may then be applied to the surface of the substrate by conventionally known methods. Any electrically conductive substrate may be employed. Preferred electrically conductive substrates include but are not limited to glassy carbon, graphite, graphene, iron, copper, aluminum, gold, silver, platinum, and any electrically conductive polymers mentioned herein above.

[0089] Suitable binders known to one of ordinary skill which are chemically stable in the potential window of use of an electrochemical cell or supercapacitor may include thermoplastics and thermosetting resins. For example, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene rubber, a tetrafluoroethylene hexafluoroethylene copolymer, a tetrafluoroethylene hexafluoropropylene copolymer (FEP), a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE resin), polychlorotrifluoroethylene resin (PCTFE), a propylene-tetrafluoroethylene copolymer, an ethylene-chlorotrifluoroethylene copolymer (ECTFE). Additionally, water soluble binders including branched polyethyleneimine (bPEI), an ethylene-acrylic acid copolymer such as poly 2-acrylamido-2-methylpropane sulfonic acid (PAMPS) and Nafion may be employed as binder. These binders may be used independently, or mixtures may be used.

[0090] In some preferred embodiments, the binder is a conductive polymer, also described as electroactive polymer. The conductive polymers comprise inherently conductive polymers (ICP) and conductive plastics. The latter are traditional plastics, such as thermoplastics, that may include conductive fillers, such as powdered metals or carbon (e.g., carbon black or fiber). The conductive polymer may be a biocompatible conductive polymer that isionically conductive and that is mechanically stable over a desired period of time, such as, for example, polypyrrole. In further embodiments the conductive polymer may include, for example, polynaphthalene, polythiophene, Nafion, polyethylene oxide, and polyethyldioxythiophene (PEDOT). Other classes of conductive polymers include polyacetylenes, conductive polypyrrole polystyrene sulfonate, polythiophenes (PT), and polyanilines. Conductive polymers may also include EHPT (poly(3-(2-ethylhexyl)thiophene), ionomers (e.g., Nafion), poly(3,4 ethylene dioxythiophene) (PEDOT) and PEDOT polystyrene sulfonate(PSS/PEDOT).

[0091] In some embodiments, Nafion is used as a binder which is a trade name for sulfonated tetrafluoroethylene based fluoropolymer-copolymer having the chemical formula C.sub.7HF.sub.13OSC.sub.2H.sub.4. This polymer's ionic properties are a result of incorporating perfluorovinyl ether groups terminated with sulfonate groups onto a tetrafluoroethylene (PTFE) backbone. Nafion can be used as a proton conductor for proton exchange membrane (PEM) fuel cells because of its excellent thermal and mechanical stability. It can be produced as both a powder resin and a copolymer. It has various chemical configurations and thus, several chemical names in the IUPAC system. Nafion-H, for example, includes the following systematic names in Chemical Abstract including ethanesulfonyl fluoride, 2-[1-[difluoro-[(trifluoroethenyl)oxy]methyl]-1,2,2,2-tetrafluoroethoxy]-1,1,2,2,-tetrafluoro-, with tetrafluoroethylene; and tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer. The molecular weight of Nafion may vary due to differences in processing and solution morphology. A preferred structure for a Nafion unit is:

##STR00001##

This structure illustrates the variability of the material; for example, the most basic monomer contains chain variation between the ether groups (the z subscript). The molecular weight has been estimated at 105-106 Da. Equivalent weight (EW) and material thickness are used to describe most commercially available Nafion membranes. The EW is the number of grams of dry Nafion per mole of sulfonic acid groups when the material is in the acid form.

[0092] In some embodiments of the method, the binder is added to a suspension of the catalyst in aqueous organic solvent in an amount in the range of 0.001-0.010 wt. %, preferably in the range in the range of 0.002-0.008 wt. %, preferably in the range of 0.003-0.006 wt. %, in the range of 0.004-0.005 wt. % of the weight of the catalyst to form a mixture. Any volatile organic solvent miscible with water may be used such as methanol, ethanol, propanol, isopropanol, acetone and the like may be used as a solvent to obtain the mixture. The mixture is deposited on the surface of the substrate and the solvent is allowed to evaporate and the process is repeated until the desired catalyst loading is achieved.

[0093] In some embodiments, the method for modifying electrically conductive substrates of invention comprises preparing a slurry of the porous nitrogen doped carbon nanosheets of the invention in an aqueous ethanol containing an electrically conductive binder disclosed herein such as, but not limited to, tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer (Nafion) in an amount in the range of 0.001 wt. % to 0.01 wt. %, sonicating the slurry to form a suspension, depositing the suspension on the surface of an electrically conductive substrate, air drying the deposited suspension on the electrically conductive substrate, and repeating the depositing and drying steps until a catalyst loading of 0.2-10 mg/cm.sup.2.

[0094] Another aspect of the invention is directed to an electrochemical cell comprising at least one electrically conductive substrate of the invention as an electrode. Typically, an electrochemical cell comprises a working electrode, a counter electrode and an electrolyte, wherein the electrolyte covers the surfaces of the electrodes. In some preferred embodiments, the electrolyte is aqueous acid or alkali or alkaline earth metal hydroxide solution. Any mineral acid may be utilized such as but not limited to hydrochloric acid, sulfuric acid, and nitric acid. In a preferred embodiment sulfuric acid is used as an electrolyte. Any alkali or alkaline earth metal hydroxide such as but not limited to lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and the like may be used as an electrolyte. The concentration of the electrolyte in cell is in the range of 0.1-2.0 M, preferably in the range of 0.2-1.8 M, preferably in the range of 0.3-1.5, preferably in the range of 0.4-1.2, and preferably in the range of 0.5-1.0 M. In particularly preferred embodiments, the electrolyte is sulfuric acid at a concentration of about 1.0 M. In some other preferred embodiment, the electrolyte is potassium or sodium hydroxide at a concentration of about 1.0M.

[0095] In some other embodiment, the electrolyte is a solid electrolyte. There are several forms of solid electrolytes that include but are not limited to gel electrolyte and solid electrolyte. Gel electrolytes resemble closely liquid electrolytes. In essence, they are liquids in a flexible lattice framework. They are formed by dissolving a salt in a polar liquid and adding polymer network to give the material mechanical stability. Examples of gel electrolytes include, but not limited to sodium acetate or sulfate/polyvinyl alcohol/polyethylene oxide, lithium trifluoromethane sulfonic acid in poly(vinylidene fluoride), poly(1-vinyl-3-propylimidazolium bis(fluorosulfonyl)imide)/1-ethyl-3-methyl imidazolium bis(fluorosulfonyl)imide (EMIFSI), and the like. Dry polymer electrolytes differ from liquid and gel electrolytes in that salt is directly dissolved into the solid medium. Examples of such polymers include, but not limited to polyethers, polyesters, polyimines, polythiols, polysiloxane, and combination thereof. In order to increase the mechanical strength and conductivity of such electrolytes, composites are used in combination with an inert ceramic phase. There are two major classes of such electrolytes: polymer-in-ceramic and ceramic-in-polymer. In solid ceramic electrolytes, ions migrate through the ceramic phase by means of vacancies or interstitials within the lattice. Also, there are glassy-ceramic electrolytes. Another type of solid electrolyte is an organic ionic plastic crystal which is a type of organic salts exhibiting mesophases, i.e., a state of matter intermediate between liquid and solid. In such an electrolyte, mobile ions are orientationally or rotationally disordered while their centers are located at ordered sites in a crystal structure. They have various forms of disorder due to one or more solid-solid phase transitions below the melting point, and therefore, have plastic properties and good mechanical flexibility as well as improved electrodeelectrolyte interfacial contact. In particular, protic organic ionic plastic crystals (POIPCs), which are solid protic organic salts formed by proton transfer from a Brnsted acid to a Brnsted base and in essence are protic ionic liquids in the molten state, have found to be promising solid-state proton conductors for fuel cells. Examples include 1,2,4-triazolium perfluorobutanesulfonate and imidazolium methanesulfonate.

[0096] Another aspect of the invention is directed to a supercapacitor comprising the modified electrically conductive substrate of the invention. A supercapacitor, also called an ultracapacitor, is a high-capacity capacitor with a capacitance value much higher than other capacitors with lower voltage limits, that bridges the gap between electrolytic capacitors and rechargeable batteries. Typically, it stores 5 to 500 times, preferably 10-400, preferably 15-300, preferably 20-200, preferably 30-100 more energy per unit volume or mass than electrolytic capacitors, can accept and deliver charge much faster than batteries, and tolerates many more charge and discharge cycles than rechargeable batteries. Supercapacitors are used in applications requiring many rapid charge/discharge cycles, rather than long term compact energy storage system such as, but not limited to automobiles, buses, trains, cranes, and elevators. Smaller units are used as memory backup for static random-access memory (SRAM).

[0097] Unlike ordinary capacitors, supercapacitors do not use the conventional solid dielectric material, but rather, they use electrostatic double-layer capacitance and electrochemical pseudocapacitance, both of which contribute to the total capacitance of the capacitor, with a few differences: Electrostatic double-layer capacitors (EDLCs) utilize carbon electrodes or derivatives thereof with much higher electrostatic double-layer capacitance than electrochemical pseudocapacitance, achieving separation of charge in a Helmholtz double layer at the interface between the surface of a conductive electrode and an electrolyte. The separation of charge is on the order of a few Angstroms (0.3-0.8 nm), much smaller than in a conventional capacitor. Electrochemical supercapacitors consist of two electrodes separated by an ion-permeable membrane (separator), and an electrolyte ionically connecting to both electrodes. When the electrodes are polarized by an applied voltage, ions in the electrolyte form electric double layers of opposite polarity to the electrode's polarity. For example, positively polarized electrodes will have a layer of negative ions at the electrode/electrolyte interface along with a charge-balancing layer of positive ions adsorbing onto the negative layer. The opposite is true for the negatively polarized electrode. Additionally, depending on electrode material and surface shape, some ions may permeate the double layer becoming specifically adsorbed ions and contribute with pseudocapacitance to the total capacitance of the supercapacitor. The supper capacitor of the invention comprises at least one electrode which is the modified electrically conductive substrate of invention.

[0098] The examples below are intended to further illustrate protocols for the method of dehydrogenating the butane-containing hydrocarbon stream and the method of producing the bimetallic catalyst, and are not intended to limit the scope of the claims.

Example 1

Materials and Methods:

[0099] The chemicals used were obtained from Sigma Aldrich. The Albizia plant leaves were collected from trees around building 28, at King Fahad University of Petroleum and Minerals, DhahranSaudi Arabia. Nitrogen (N.sub.2) gas (99.99% purity) was supplied by the SCG gas supplier center, Jubail, Saudi Arabia.

Preparation of Nitrogen-Doped Carbon Materials from Albizia procera Leaves:

[0100] Scheme I of FIG. 1 outlines the method of preparing the nitrogen doped carbon material of the invention. Typically, collected leaves of Albizia procera were washed using tap water and dried for two days under the sun followed by drying in an oven for 48 h at 100 C. Using a kitchen blender, the dried leaves were pulverized to obtain a fine powder. NaHCO.sub.3 and ZnCl.sub.2 were used as activating agents to obtain carbon with a high surface area. A sample of lea powder (3 g) was mixed with NaHCO.sub.3 in a mass ratio of 1:2, and another sample was mixed with ZnCl.sub.2 in a mass ratio of 1:4. The leaf powder, with or without activating agent, was heated in a tube funace at 850 C. under a nitrogen atmosphere for 5 h. The heating and cooling rates were 10 C./min and 5 C./min, respectively. After cooling to room temperature, each carbonized sample was washed by ultra-sonication in an aqueous solution of 1 M HCl, and subsequent centrifugation was used to remove all metals and other soluble impurities. Then, each sample was washed with deionized water and filtered using filter paper. As a final step, samples were dried in an oven at 60 C. for 24 h. The dried nitrogen-doped carbon materials prepared without an activating agent and with the activating agents NaHCO.sub.3 and ZnCl.sub.2 are designated WANC, NaNC, and ZnNC, respectively.

Example 2

BET Surface Area and Pore Size Distribution:

[0101] The pore size distribution and the specific surface area were investigated using the nitrogen adsorption-desorption method (BET: Micromeritics, ASAP 2020). The surface properties of a carbon electrode are useful for enhancing supercapacitor performance. ZnCl.sub.2 and NaHCO.sub.3 were each used to increase the specific area of the carbon electrodes. FIG. 2 shows the nitrogen isothermal analysis for the three prepared carbon samples, WANC, NaNC, and ZnNC, which was performed to determine their pore structures. It can be clearly seen that the three samples belong to type-IV isothermal sorption curves due to the presence of hysteresis loops. In such a curve type, the initial part of the curve is attributed to micropores, and the latter part is due to the existence of mesopores [Sing, K. S. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984) Pure and applied chemistry (1985) 57, 603-619incorporated herein by reference in its entirety]. In addition, the observed significant increase in the NaNC loop size in the relative pressure range (P/P.sub.0=0.80-1.00), a Type H3 loop, indicates the presence of macropores [Sun et al. Nitrogen-doped porous carbons derived from polypyrrole-based aerogels for gas uptake and supercapacitors ACS Applied Nano Materials (2018) 1, 609-616; and Thommes et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report) Pure and Applied Chemistry (2015) 87,1051-1069each incorporated herein by reference in their entirety]. Comparing the three results, NaNC shows the highest specific surface area of 910 m.sup.2/g, followed by ZnNC and WANC with surface areas of 777 m.sup.2/g and 322 mf, respectively. As a result, NaNC was expected to be the best electrode material for supercapacitor applications among the prepared nitrogen-doped carbon materials. NaNC had nearly three times the sorption volume of WANC, although the average pore width of WANC (49 ) was larger than that of NaNC (28 ), which indicates NaNC has a higher micro/mesopore ratio than WANC. Table 1 summarizes the BET surface area and average pore width results for the three synthesized carbon samples.

TABLE-US-00001 TABLE 1 BET surface area and average pore diameter of the different carbon structures Average pore BET surface area Carbon sample diameter () m.sup.2/g WANC 49 322 ZnNC 15 777 NaNC 28 910

Example 3

Raman Spectral Analysis:

[0102] Raman spectra were recorded on iHR320 Raman spectrometer equipped with CCD detector, HORIBA. Raman spectral analysis is widely used to characterize the structural features of carbonaceous materials [Sadezky et al. Raman microspectroscopy of soot and related carbonaceous materials: spectral analysis and structural information Carbon (2005) 43, 1731-1742; and Marsh et al. Activated carbon Elsevier, (2006)each incorporated herein by reference in their entirety]. FIG. 3 shows the Raman spectra of the activated carbon samples WANC, NaNC and ZnNC. All samples show the typical Raman spectrum of carbon materials with two prominent peaks observed at ca. 1358 cm.sup.1 corresponding to the D-band indicating disorganized carbon and ca. 1600 cm.sup.1 corresponding to the G-band indicating graphitic carbon. All samples spectra show troughs with a high signal intensity between the D-band and -G band, which can be classified as the peak D3 band (ca. 1500 cm.sup.1), indicating the presence of amorphous carbon. The D band and G band in all samples spectra are broad, which can be attributed to higher disorder in graphite [Jawhari et al. Raman spectroscopic characterization of some commercially available carbon black materials Carbon (1995) 33, 1561-1565; and Aziz et al. A Simple and Direct Preparation of a Substrate-Free Interconnected Nanostructured Carbon Electrode from Date Palm Leaflets for Detecting Hydroquinone ChemistrySelect (2017) 2, 4787-4793each incorporated herein by reference in their entirety].

Example 4

X-Ray Analysis:

[0103] X-ray diffraction patterns were obtained on Rigaku Miniflex 600 diffractometer to study the crystallinity of the activated carbon samples. The experiments were conducted in 20 range from 10 to 70 as shown in FIG. 4. The diffraction patterns of the three samples display broad peaks at 29=24.7 and 44.3 that can be attributed to (002) and (100) planes, respectively, indicating the amorphous nature of all the carbon samples [Li et al. X-ray diffraction patterns of graphite and turbostratic carbon Carbon. 2007, 45, 1686-1695-incorporated herein by reference in its entirety]. The diffraction peaks present in the WANC and NaNC diffraction patterns can be attributed to partial crystallization of the carbon because the positions of the peaks are very similar to the peaks in the diffraction pattern of graphite [Ariharan et al. Nitrogen doped graphene as potential material for hydrogen storage Graphene (2017) 6, 41incorporated herein by reference in its entirety].

Example 5

Surface Morphology:

[0104] The morphologies of the prepared carbon materials were evaluated by both scanning electron microscopy (SEM, Tescan Lyra 3, Czech Republic) and transmission electron microscopy (TEM, JEOL, JEM 2011). The nitrogen-doped carbon prepared with or without activating agent was studied using SEM and TEM to ascertain the surface morphology of the prepared samples. FIGS. 5A, 5C, and 5E show SEM images of WANC, ZnNC, and NaNC SEM respectively, and FIGS. 5B, 5D, and 5F show TEM images of WANC, ZnNC, and NaNC, respectively. The figures mentioned above show the porosity improvement of surface by using an activating agent. FIGS. 5A and 5B demonstrate the bulk nature of WANC, which in turn explains the low surface area of carbon material. Using ZnCl.sub.2 as an activation agent increases the carbon surface topography, as shown in FIGS. 5C and 5D by the appearance of some small-sized pores. However, the use of NaHCO.sub.3 increases both the size and number of pores on the surface of NaNC carbon significantly, as shown in FIGS. 5E and 5F, and thereby increasing the specific surface area. That is consistent with the BET results discussed above. NaNC is composed of carbon nanosheets with numerous macropores, which correlates with the BET data discussed above.

Example 6

Chemical Composition and Functional Groups:

[0105] X-ray photoelectron spectroscopy (XPS: Model: ESCALAB250Xi) was used to examine the chemical composition of the prepared activated carbon materials. FTIR spectra were obtained on Thermo Scientific NICOLET 6700 spectrometer to identify the functional groups present and the microstructure of the activated carbon samples. FTIR spectra of the three samples were recorded in the range of 4000-400 cm.sup.1 with 32 scans per spectrum at 4 cm.sup.1 resolution. To prepare the sample pellet for FTIR spectral analysis, 0.1 wt. % of the carbon sample was mixed with potassium bromide (KBr) (Thermo Fisher Scientific) powder to prepare KBr pellets. The pellet was formed by transferring the sample powder into a 20 mm die and applying 4-ton pressure using an ATLAS POWER T25 PRESS.

[0106] The functional groups and chemical composition of the carbon materials play significant role in supercapacitor applications. As a result, the chemical compositions and functional groups present on the surface of the nitrogen-doped carbon materials were studied using XPS and FTIR techniques.

[0107] NaNC sample was selected for further examination by XPS because it has the largest BET surface area. FIG. 6A shows the XPS of NaNC displaying three distinct peaks appear at 284.6, 397.5, and 531.8 eV. They are attributed to carbon (C is), nitrogen (N is), and oxygen (O Is), respectively. Quantitative elemental analyses of WANC, ZnNC, and NaNC show that the composition percentages are 90% C 1s, 5.5% O 1s, 3% N Is, and 1.5% other impurities.

[0108] FIG. 6B shows the XPS spectra for C Is. Deconvolution of the C is spectrum shows four distinct peaks with binding energies at 284.6, 285.6, 286.3, and 288.4 eV (see FIG. 6B) related to sp.sup.2 CC and CC graphitic carbon, CO phenol or alcohol bonding, CN linkage, and ester linkages, respectively [Goel et al. Synthesis of nitrogen doped mesoporous carbons for carbon dioxide capture RSC Advances. 2015, 5, 46568-46582incorporated herein by reference in its entirety]. Deconvoluted O is spectrum shown in FIG. 6C displays the binding energies related to CO groups at 529.2 eV and COC or COH groups at 531.8 eV [Biniak et al. The characterization of activated carbons with oxygen and nitrogen surface groups Carbon (1997) 35, 1799-1810incorporated herein by reference in its entirety]. FIG. 6D shows the three deconvoluted peaks of N is centered at 398.6, 400.1, and 401.3 eV, which can be attributed to pyridinic, pyrrolic and/or pyridonic nitrogen (Goel et al.).

[0109] FIG. 7 shows the FTIR spectra of the activated carbon samples, WANC, ZnNC, and NaNC. All spectra show similar vibration bands characteristic of activated carbon materials [Hesas et al. Preparation and characterization of activated carbon from apple waste by microwave-assisted phosphoric acid activation: application in methylene blue adsorption BioResources. (2013) 8, 2950-2966-incorporated herein by reference in its entirety]. The FTIR spectra of all samples show absorption in the region 3500-3000 cm.sup.1 corresponding to hydroxyl structures [Larkin, P. General outline and strategies for IR and Raman spectral interpretation. IR and Raman Spectroscopy: Principles and Spectral Interpretation (2011) 117-134incorporated herein by reference in its entirety. The broad absorption band with a peak at ca. 3430 cm.sup.1 is attributed to the OH stretching vibration of hydroxyl groups and adsorbed water. Also, the peak 3100-3500 cm.sup.1 can be attributed to NH stretching vibration. Noticeably, ZnNC shows a sign of a reduction in hydrogen bonding, as reflected by the small OH stretching band at ca. 3430 cm.sup.1. The band observed between ca. 1750 and 1500 cm.sup.1 and centered ca. 1630 cm.sup.1 corresponds to olefinic group (CC, 1850-1500 cm.sup.1)/(CN) [Huang et al. Highly efficient magnetic nitrogen-doped porous carbon prepared by one-step carbonization strategy for Hg.sup.2+ removal from water ACS applied materials & interfaces. 2017, 9, 2550-2559, and Clougherty et al. CN stretching frequency in infrared spectra of aromatic azomethine. The Journal of Organic Chemistry. 1957, 22, 462each incorporated herein by reference in its entirety]. The intense absorption band centered at ca. 1086 cm.sup.1 can be assigned to CO stretching (CO, 850-1300 cm.sup.1) or CN stretching (1080-1360 cm.sup.1), see Larkin, P. The small broad band observed between 3000-2800 cm.sup.1 in the spectra of WANC and NaNC can be attributed to the adsorption of an aliphatic group (CH). The band appearing in the NaNC spectrum at ca. 2082 cm.sup.1 can be attributed to a carbon-carbon triple bond (CC), triple and cumulated double bond stretch usually appears as a weak band from 2260-2100 cm.sup.1, see Larkin P. Overall, it is very difficult to differentiate the oxygen and nitrogen containing functional groups in the synthesized carbon samples by FTIR as the peaks overlap. This phenomenon was realized in the reported FTIR spectra of graphene oxide and N-doped graphene oxide [Kumar et al. Plasma-assisted simultaneous reduction and nitrogen doping of graphene oxide nanosheets Journal of Materials Chemistry A. 2013, 1, 4431-4435incorporated herein by reference in its entirety].

Example 7

Electrochemistry

Preparation of Working Electrodes:

[0110] Twenty milligrams of each of the prepared carbon samples was mixed separately with 5 mL of ethanol, sonicated for 1 h, then mixed with 30 L of Nafion, which was used as a binding material, and finally sonicated for another 30 min. On a steel foil (2 cm1 cm), 300 L of the solutions was dropped and the ethanol was evaporated to obtain the working electrodes. Finally, the electrodes were dried at 60 C. for 2 h.

Electrochemical Measurements:

[0111] Electrochemical measurements were performed using a CHI 760E potentiostat in a three-electrode configuration comprising a counter electrode (platinum foil), a working electrode coated with nitrogen doped carbon, and a standard reference electrode (Ag/AgC). A solution of 1 M H.sub.2SO.sub.4 was utilized as the aqueous electrolyte for the cell. Cyclic voltammetry (CV) measurements at different scanning rates were conducted. Galvanostatic charge-discharge (GCD) measurements were performed at different current densities for the three samples to examine their capacity and test their stability over thousands of cycles. The specific capacitance was calculated using formulas 1 and 2 for CV and GCD, respectively [Zhu et al. Effects of various binders on supercapacitor performances Int J Electrochem Sci (2016) 11, 8270-8279incorporated herein by reference in its entirety].

C=IdV/mV(1)

C=It/mV(2)

where C is the specific capacitance (Fg.sup.1), I is the applied current density (A g.sup.1), t is the time required for discharging (s), m is the carbon mass loaded on the electrode (g), V is the voltage range for charging and discharging (V), and v is the potential scan rate (V/s).

[0112] Cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) measurements were performed with the three carbon electrodes to study their supercapacitance performance. FIGS. 8A and 8B compare the performances of each of the three prepared samples. The CV curves shown in FIG. 8A of WANC, ZnNC, and NaNC have a nearly rectangle-like shape exhibiting typical EDLC mechanism [Wang et al. Three-dimensional flower-like and hierarchical porous carbon materials as high-rate performance electrodes for supercapacitors Carbon. (2014) 67, 119-127; Tang et al. A high energy density asymmetric supercapacitor from nano-architectured Ni(OH).sub.2/Carbon nanotube electrodes Advanced Functional Materials (2012) 22, 1272-1278; and Karthikeyan et al. A novel asymmetric hybrid supercapacitor based on Li.sub.2FeSiO.sub.4 and activated carbon electrodes Journal of Alloys and Compounds (2010) 504, 224-227each incorporated herein by reference in their entirety]. In addition, the NaNC electrode shows two small broad peaks near 0.3 and 0.6 V, implying Faradaic redox reactions or pseudocapacitive behavior due to the presence of oxygen- and nitrogen-containing functional groups in NaNC. As mentioned previously, the main purpose of the activation process is to increase the specific surface area of the carbon electrode, which has a significant role in boosting the specific capacity of the double layer capacitance of the electrode. As expected, WANC and ZnNC, which have a lower specific surface area compared to NaNC, exhibit smaller specific capacitances of 35.9 F g.sup.1 and 53.4 F g.sup.1, respectively, at a 20 mV/s scan rate. In contrast, NaNC shows specific capacitance of 160.2 F g.sup.1. Similar behavior was observed in the charging-discharging measurements, as shown in FIG. 8B. NaNC has the highest discharging rate and hence, the largest specific capacitance. At 2 A g.sup.1, NaNC has a specific capacitance value of 214.5 F g.sup.1, whereas WANC and ZnNC have specific capacitance of 19.1 F g.sup.1 and 30.3 F g.sup.1, respectively. In addition to the high specific surface area, the large capacitance value of NaNC could be attributed to its good conductivity due to the oxygen- and nitrogen-containing functional groups of the activated carbon [Suktha et al. High-performance supercapacitor of functionalized carbon fiber paper with high surface ionic and bulk electronic conductivity: effect of organic functional groups Electrochimica Acta (2015) 176. 504-513; and Cheng et al. Synergistic effects from graphene and carbon nanotubes enable flexible and robust electrodes for high-performance supercapacitors Nano letters. 2012, 12, 4206-4211each incorporated herein by reference in their entirety]. NaHCO.sub.3-activated carbon was further investigated at different scan rates and different current densities. FIG. 9A displays the CV measurements of NaNC at scan rates of 5, 10, 20, and 50 mV s.sup.1. The specific capacitances were 225.8 F g.sup.1, 198.6 F g.sup.1, and 160.2 F g.sup.1 at scan rates of 5, 10 and 20 mV s.sup.1, respectively. At scan rate of 50 mV s.sup.1, the CV curve shows a distorted rectangular shape, but it has a specific capacitance of 104.8 F g.sup.1, indicating good capacitance performance even at high scanning rates.

[0113] GCD curves of NaNC were obtained to examine the electrochemical performance of the capacitor at different applied current densities, as shown in FIG. 9B. Curves show a quasi-triangular shape, revealing ideal EDLC behavior [Yang et al. All solid-state electric double-layer capacitors based on alkaline polyvinyl alcohol polymer electrolytes Journal of power sources (2005) 152, 303-310incorporated herein by reference in its entirety]. A specific capacitance of 231.2 F g.sup.1 was achieved at an applied current density of 1 A g.sup.1. By increasing the value of the applied current density to 2 A g.sup.1, 5 A g.sup.1, and 10 A g.sup.1, the specific capacitance decreased to 214.5 F g.sup.1, 166.7 F g.sup.1, and 108.8 F g.sup.1, respectively. The decreasing trend in the specific capacitance with increasing applied current density is attributed to insufficient electrolyte ion diffusion on the carbon electrode surface at higher current densities [Mondal et al. Nitrogen-Doped Porous Carbon Nanosheets from Eco-Friendly Eucalyptus Leaves as High Performance Electrode Materials for Supercapacitors and Lithium Ion Batteries Chemistry A European Journal. (2017) 23, 3683-3690incorporated herein by reference in its entirety]. FIG. 9C demonstrates the first 20 charging-discharging cycles of 1000 cycles for NaNC. The cycles have similar curves, indicating stability and excellent electrochemical performance. FIG. 9D shows 97.3% retention of specific capacitance even after 1000 charging-discharging cycles, confirming the high stability of the NaNC electrode. Table 2 summarizes the specific capacitances of the three carbon electrodes, WANC, ZnNC, and NaNC. Table 3 compares the specific capacitance of NaNC (231.2 F g.sup.1) to those previously reported carbon electrodes prepared from different biomass feedstocks.

TABLE-US-00002 TABLE 2 Specific capacitance of the three carbon electrodes, WANC, ZnNC, and NaNC CV Measure- ment at Scanning rate GDC at Current Density of 20 mV/s of 2 A/g Electrode F/g F/g WANC 35.9 19.1 ZnNC 53.4 30.3 NaNC 160.2 214.5 Specific capacitance of NaNC Electrode Measured by CV Scanning rate 5 mV/s 10 mV/s 20 mV/s 50 mV/ F/g 225.8 F g.sup.1 198.6 F g.sup.1 160.2 F g.sup.1 104.8 F g.sup.1 Specific capacitance of NaNC Electrode Measured by GDC Current 1 2 5 10 density, A/g F/g 231.2 214.5 166.7 108.8

TABLE-US-00003 TABLE 3 Comparison of the specific capacitance of NaNC with that of previously reported carbon prepared from different biomasses Biomass Surface Specific waste (car- Activatin area capaci- Measurement bon source) g agent (m.sup.2/g) tance (F/g) conditions Ref Giant KOH 2212 121 1M TEABF4, 1 Miscanthus 0.5 mA/cm.sup.2 Coffee CO.sub.2 709 176 1M H.sub.2SO.sub.4, 10 mA 2 endocarp Bamboo KOH >3000 >300 1M KOH, 1 A/g 3 Coconut ZnCl.sub.2 2440 246 0.5 M H.sub.2SO.sub.4, 4 shells 0.25 A/g Potato waste ZnCl.sub.2 1052 255 2M KOH, 1 A/g 5 Rice straw H.sub.3PO.sub.4 376.65 112 1M H.sub.2SO.sub.4, 2 mV/s 6 Teak wood ZnCl.sub.2 2108 131 1M LiPF.sub.6, 0.1 A/g 7 Broad beans KOH 655.4 202 6M KOH, 0.5 A/g 8 Banana fiber ZnCl.sub.2 1097 74 1M Na.sub.2SO.sub.4, 0.5 A/g 9 A. procera NaHCO.sub.3 910 231 1M H.sub.2SO.sub.4, 1 A/g This work

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