PRODUCTION OF CARBON-BASED OXIDE AND REDUCED CARBON-BASED OXIDE ON A LARGE SCALE

Abstract

Provided herein are carbon-based oxide (CBO) materials and reduced carbon-based oxide (rCBO) materials, fabrication processes, and devices with improved performance and a high throughput. In some embodiments, the present disclosure provides materials and methods for synthesizing CBO and rCBO materials. Such methods avoid the shortcomings of current synthesizing methods to facilitate facile, high-throughput production of CBO and rCBO materials.

Claims

1. A method for producing a carbon-based oxide material comprising: forming a first solution comprising graphite and an acid; cooling the first solution to a first temperature; adding a first oxidizing agent to the first solution to form a second solution; and quenching the second solution to a second temperature to form a carbon-based oxide material.

2. The method of claim 1, wherein the acid comprises perchloric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, or any combination thereof.

3. The method of claim 1, wherein the mass of the acid is greater than the mass of the graphite by a factor of about 30 to about 180.

4. The method of claim 1, wherein the first temperature is about −20° C. to about 30° C.

5. The method of claim 1, wherein the first oxidizing agent comprises oxygen, ozone, hydrogen peroxide, fluorite dioxide, lithium peroxide, barium peroxide, fluorine, chlorine, nitric acid, nitrate compounds, sulfuric acid, peroxydisulfuric acid, peroxymonosulfuric acid, chlorite, chlorate, perchlorate, halogen compounds hypochlorite, hypohalite compounds, household bleach, hexavalent chromium compounds, chromic acids, dichromic acids, chromium trioxide, pyridinium chlorochromate, chromate compounds, dichromate compounds, permanganate compounds, potassium permanganate, sodium perborate, nitrous oxide, potassium nitrate, sodium bismuthate, or any combination thereof, and wherein the mass of the first oxidizing agent is greater than the mass of the graphite by a factor of about 1.5 to about 12.

6. The method of claim 1, wherein the first oxidizing agent is added to the first solution over a period of time of about 15 minutes to about 180 minutes.

7. The method of claim 1, wherein a temperature of the second solution during the addition of the first oxidizing agent is less than about 30° C.

8. The method of claim 1, further comprising allowing the second solution to react at a third temperature over a first period of time wherein the third temperature is about 10° C. to about 70° C., and wherein the first period of time is about 15 minutes to about 120 minutes.

9. The method of claim 1, wherein the second solution is quenched to the second temperature by an ice bath, a water bath, one or more cooling coils, ice, water, by adding a second oxidizing agent to the second solution, or any combination thereof, and wherein the second temperature is about 25° C. to about 75° C.

10. The method of claim 1, wherein quenching the second solution occurs over a period of time of about 30 minutes to about 120 minutes.

11. The method of claim 9, wherein the second oxidizing agent comprises oxygen, ozone, hydrogen peroxide, fluorite dioxide, lithium peroxide, barium peroxide, fluorine, chlorine, nitric acid, nitrate compounds, sulfuric acid, peroxydisulfuric acid, peroxymonosulfuric acid, chlorite, chlorate, perchlorate, halogen compounds hypochlorite, hypohalite compounds, household bleach, hexavalent chromium compounds, chromic acids, dichromic acids, chromium trioxide, pyridinium chlorochromate, chromate compounds, dichromate compounds, permanganate compounds, potassium permanganate, sodium perborate, nitrous oxide, potassium nitrate, sodium bismuthate, or any combination thereof, and wherein a mass of the second oxidizing agent is greater than the mass of the graphite by a factor of about 1.5 to about 6.

12. The method of claim 1, further comprising agitating at least one of the first solution, and the second solution for a period of time of about 45 minutes to about 360 minutes.

13. The method of claim 1, further comprising allowing the second solution to react for a period of time of about 15 minutes to about 120 minutes after the second solution is quenched, wherein the second solution during reaction has a temperature that is about 15° C. to about 75° C.

14. The method of claim 1, further comprising purifying the second solution, purifying the second solution comprises filtering the carbon-based oxide material through a filter and concentrating the carbon-based oxide material.

15. The method of claim 14, wherein the carbon-based oxide material is filtered until its pH is about 3 to about 7.

16. The method of claim 1, further comprising: forming a third solution comprising the carbon-based oxide material and a third oxidizing agent; heating the third solution to a fourth temperature for a period of time; and adding a mineral ascorbate to the third solution to form a reduced carbon-based oxide material.

17. The method of claim 16, wherein heating the carbon-based oxide material to the fourth temperature, and adding a first quantity of the third oxidizing agent to the carbon-based oxide material, occur simultaneously.

18. The method of claim 16, wherein the fourth temperature is about 45° C. to about 180° C., and wherein heating the third solution to a fourth temperature occurs over a period of time of about 30 minutes to about 120 minutes.

19. The method of claim 16, wherein the third oxidizing agent comprises oxygen, ozone, hydrogen peroxide, fluorite dioxide, lithium peroxide, barium peroxide, fluorine, chlorine, nitric acid, nitrate compounds, sulfuric acid, peroxydisulfuric acid, peroxymonosulfuric acid, chlorite, chlorate, perchlorate, halogen compounds hypochlorite, hypohalite compounds, household bleach, hexavalent chromium compounds, chromic acids, dichromic acids, chromium trioxide, pyridinium chlorochromate, chromate compounds, dichromate compounds, permanganate compounds, potassium permanganate, sodium perborate, nitrous oxide, potassium nitrate, sodium bismuthate, or any combination thereof, and wherein the mass of a second quantity of the third oxidizing agent is greater than the mass of the graphite by a factor of about 1.1 to about 6.

20. The method of claim 16, wherein the mineral ascorbate comprises sodium ascorbate, calcium ascorbate, potassium ascorbate, magnesium ascorbate, or any combination thereof.

21. The method of claim 16, wherein the mass of the mineral ascorbate is greater than the mass of the graphite by a factor of about 2 to about 10.

22. The method of claim 16, wherein the mineral ascorbate is added to the third solution over a period of time of about 10 minutes to about 60 minutes.

23. The method of claim 16, further comprising allowing the third solution and the mineral ascorbate to react for a period of time of about 45 minutes to about 180 minutes.

24. The method of claim 16, further comprising agitating the third solution for a period of time of about 45 minutes to about 360 minutes.

25. The method of claim 16, further comprising purifying the reduced carbon-based oxide material, wherein purifying the reduced carbon-based oxide material comprises filtering with a second filter, flushing the third solution, or any combination thereof.

26. The method of claim 16, capable of producing a throughput of carbon-based oxide material of about 0.1 pound/day to about 50 pounds/day.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0077] Novel features of the disclosure are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present disclosure will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the embodiments are utilized, and the accompanying drawings or figures (also “FIG.” and “FIGs.” herein), of which:

[0078] FIG. 1 illustratively depicts a diagram of a first exemplary method of producing carbon-based oxide (CBO) or reduced carbon-based oxide (rCBO) materials, per embodiments described herein.

[0079] FIG. 2 illustratively depicts a diagram of a second exemplary method of producing CBO or rCBO materials, per embodiments described herein.

[0080] FIG. 3 is an exemplary graph showing the relationship between the capacitance and the reaction time, and the relationship between the reaction temperature and the reaction time, per embodiments described herein.

[0081] FIG. 4 is an exemplary graph showing the relationship between the capacitance and the reaction time, and the relationship between the reaction temperature and the reaction time, per embodiments described herein.

[0082] FIG. 5 is an exemplary graph showing the relationship between the capacitance and the reaction time, and the relationship between the reaction temperature and the reaction time, per embodiments described herein.

[0083] FIG. 6 is a cyclic voltammetry (CV) scan of an exemplary double-layer capacitor constructed from a CBO material with a 45 min stir time, at scan rates of 10 mV/s, 20 mV/s, 40 mV/s, 60 mV/s, and 100 mV/s, per embodiments described herein.

[0084] FIG. 7A is a cyclic voltammetry (CV) scan of an exemplary double-layer capacitor with electrodes comprising light-scribed CBO materials, at a scan rate of 1,000 mV/s, per embodiments described herein.

[0085] FIG. 7B is a cyclic voltammetry (CV) scan of an exemplary double-layer capacitor with electrodes comprising light-scribed CBO materials, and non-light-scribed CBO materials, at a scan rate of 1,000 mV/s, per embodiments described herein.

[0086] FIG. 8 displays an exemplary relationship between the number HCl washes and the capacitance of the CBO material, at a scan rate of 10 mV/s, per embodiments described herein.

[0087] FIG. 9 illustratively depicts several carbon forms, per embodiments described herein.

[0088] FIG. 10 illustratively depicts an example of another carbon form, per embodiments described herein.

[0089] FIG. 11 illustratively depicts an example of yet another carbon form, per embodiments described herein.

[0090] FIG. 12 is a particle distribution chart of an exemplary CBO, per embodiments described herein.

[0091] FIG. 13 is an X-Ray Diffraction (XRD) graph of an exemplary CBO, per embodiments described herein.

[0092] FIG. 14 is an X-ray Photoelectron Spectroscopy (XPS) graph of an exemplary CBO, per embodiments described herein.

[0093] FIG. 15 is a particle size distribution chart of an exemplary rCBO, per embodiments described herein.

[0094] FIG. 16 is a Raman spectra of an exemplary rCBO, per embodiments described herein.

[0095] FIG. 17 is optical microscope image of sheets of an exemplary CBO on a silicon wafer, coated with SiO.sub.2, per embodiments described herein.

[0096] FIG. 18A is a low magnification scanning electron microscope (SEM) image of an exemplary CBO on a silicon wafer, coated with SiO.sub.2, per embodiments described herein.

[0097] FIG. 18B is a high magnification scanning electron microscope (SEM) image of an exemplary CBO on a silicon wafer, coated with SiO.sub.2, per embodiments described herein.

DETAILED DESCRIPTION

[0098] The methods herein may include procedures of making oxidized forms of carbon-based materials, procedures of making materials derived from the oxidized forms of carbon-based materials, or both. In some embodiments, the methods herein may include procedures of making oxidized forms of graphite, procedures of making materials derived from the oxidized forms of graphite, or both. The methods herein comprise procedures of making graphene/graphite oxide (GO) and reduced graphene/graphite oxide (rGO). In some embodiments disclosed herein, GO is formed from graphite in a first reaction comprising oxidation, is treated (e.g., filtered/purified, concentrated, etc.), and may be reduced (e.g., to graphene, ICCN, or any other materials derived through reduction of GO) in a second reaction. In some embodiments, the second reaction comprises reduction, wherein, for example, a GO may be reduced to form graphene, ICCN and/or other reduced forms of GO, collectively referred to herein as reduced graphite or graphene oxide (rGO).

[0099] Those skilled in the art will recognize improvements and modifications to the present disclosure. All such improvements and modifications are considered within the scope of the concepts disclosed herein.

Current Methods of Synthesizing Carbon-Based Oxide and Reduced Carbon-Based Oxide Materials

[0100] Existing methods for production of carbon-based oxide (CBO) and reduced carbon-based oxide (rCBO) materials include the Hummers method, the modified Hummers method, and various modifications thereof. Such methods are referred to herein as Hummers-based methods. Recognized herein are limitations associated with the Hummers-based methods.

[0101] In some embodiments, Hummers-based methods may be currently exhibit a low throughput, high cost, high waste quantities, and low reliability. In an example, a Hummers-based method takes about 2 months, requires several weeks of purification, costs about $93/kg, comprises expensive hydrochloric acid (HCl) washes, requires a certain technique that is left to the judgment of the individual scientist, and synthesizes a product that is often unacceptable for forming consumer grade products.

[0102] An exemplary Hummers-based method, per FIG. 1, comprises: [0103] 1. Adding 15 grams (g) graphite to 750 milliliters (mL) concentrated sulfuric acid into a reaction flask that is kept at 0° C. using ice bath. [0104] 2. Adding 90 g potassium permanganate (KMnO.sub.4) to the graphite and sulfuric acid (exothermic). [0105] 3. Removing the reaction flask from ice bath for 2 hours. [0106] 4. Returning the reaction flask into ice bath. [0107] 5. Adding 1.5 liters (L) of water (H.sub.2O) drop-wise over the course of about 1-1.5 hours while maintaining a reaction temperature at 45° C. (controlling the temperature by the rate of addition of water and by adding ice to a melting ice bath). [0108] 6. Removing the reaction flask from ice bath for 2 hours. [0109] 7. Quenching the reaction with 4.2 L H.sub.2O and then 75 mL 30% hydrogen peroxide (H.sub.2O.sub.2). [0110] 8. Purifying with five HCl washes, followed by nine H.sub.2O washes, allowing the solution to air dry for about 2 weeks, rehydrating the dried graphite oxide with water, and 2 weeks of dialysis.

Methods of Synthesizing Carbon-Based Oxide and Reduced Carbon-Based Oxide Materials

[0111] The method of the present disclosure provides for a faster, safer, cheaper, and consistent procedure for synthesizing CBO and rCBO materials. In some embodiments, the present disclosure provides procedures or methods for synthesizing graphite oxide and reduced graphite oxide (e.g., graphene, PCS, or ICCN). In contrast with other methods of making graphite oxide, the method of the present disclosure is capable of tuning the oxidation characteristics and the amount of exfoliation, is safer than other methods because the lower reaction temperatures reduce the risk of explosion, reduces the of reagents, enables expedited purification without the use of costly HCl, is configured to be fully scalable, enables increased throughput, and synthesizes a product the mechanical and electrical characteristics of which are consistent and tunable and which can be efficiently and accurately light or laser scribed.

[0112] In some embodiments, the methods described herein for synthesizing CBO and rCBO materials are safer because one or more of the reactions are performed at a temperature of less than 45° C., wherein the reactions of current methods may exceed 75° C.

[0113] In some embodiments, the method of the present disclosure is capable of synthesizing at least about 1 pound per day of a CBO or a rCBO material, including the time for purification. In some embodiments, the process is limited only by the size of the reactor, which enables the production of CBO and rCBO materials on the ton scale. In some embodiments, the methods described herein for synthesizing CBO and rCBO materials takes less than or equal to 1 week, wherein current methods require 2, 5 or 8 times as much time. In one example, the methods described herein for synthesizing CBO and rCBO materials costs about $21/kg, wherein currently available methods cost about $93/kg (a difference of more than fourfold). Further, in some embodiments, the method described herein forms less waste per mass of the CBO or rCBO materials than other methods.

[0114] In some embodiments, the method of the present disclosure provides a CBO or rCBO material whose composition (e.g., C:O atomic ratio, quantity of oxygen functionality, etc.) and/or morphology is repeatable to within about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% over a range of samples. In one example, the method of the present disclosure is capable of producing a GO with a C:O atomic ratio repeatable to within about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% over a number of batches and samples. In some embodiments, the improved reliability of the method described herein may be due to the lower reaction temperature.

[0115] In some embodiments, a method for synthesizing a CBO material (e.g., GO or PCS) comprises oxidation (first reaction), a first purification, reduction (second reaction), and a final purification. In some embodiments, a method for synthesizing an rCBO material (e.g., rGO) comprises oxidation, purification, reduction, and final purification.

[0116] In some embodiments, the process of oxidizing a carbon-based comprises a first reaction comprising: mixing graphite powder and sulfuric acid (H.sub.2SO.sub.4) while cooling the graphite powder and H.sub.2SO.sub.4 mixture to a first predetermined temperature; adding a predetermined amount of potassium permanganate (KMnO.sub.4) to the graphite powder and H.sub.2SO.sub.4 mixture to form a graphite oxidizing mixture; agitating the graphite oxidizing mixture for a predetermined amount of time (e.g., after the addition of the predetermined amount of KMnO.sub.4 has been completed); cooling the graphite oxidizing mixture to a second predetermined temperature; and adding a predetermined amount of hydrogen peroxide H.sub.2O.sub.2 and/or ice to the graphite oxidizing mixture to yield graphite oxide.

[0117] In some embodiments, the sulfuric acid and the graphite are premixed to minimize graphite dust, and are added to the reactor rapidly. In some embodiments, the mixing speed during one or more reaction processes is about 100 rpm. In some embodiments, a reaction is chilled by one or more cooling coils, ice, water, a coolant, or any combination thereof. In some embodiments, the volumes, quantities, masses, and time periods may be suitably scaled for production on a large scale.

[0118] In some embodiments, the first predetermined temperature resulting from cooling the graphite powder and H.sub.2SO.sub.4 mixture is about 0° C. In some embodiments, the first predetermined temperature resulting from cooling the graphite powder and H.sub.2SO.sub.4 mixture is about −10° C. to about 15° C. In some embodiments, the first predetermined temperature resulting from cooling the graphite powder and H.sub.2SO.sub.4 mixture is greater than or equal to about −10° C., −9° C., −8° C., −7° C., −6° C., −5° C., −4° C., −3° C., −2° C., −1° C., or 0° C. but less than or equal to about 1° C., 2° C., 3° C., 4° C., 5° C., 6° C., 7° C., 8° C., 9° C., 10° C., 11° C., 12° C., 13° C., 14° C., or 15° C.

[0119] In some embodiments, the potassium permanganate is added to the graphite powder and H.sub.2SO.sub.4 mixture at a set rate to keep the exothermic (e.g., self-heated) reaction temperature below about 15° C. In some embodiments, the reaction temperature of the graphite oxidizing mixture while adding the predetermined amount of KMnO.sub.4 to the graphite powder and H.sub.2SO.sub.4 mixture is less than or equal to about 15° C., 14° C., 13° C., 12° C., 11° C., 10° C., 9° C., 8° C., 7° C., 6° C., 5° C., 4° C., 3° C., 2° C., or 1° C. In some embodiments, the reaction temperature of the graphite oxidizing mixture while the predetermined amount of KMnO.sub.4 is added to the graphite powder and H.sub.2SO.sub.4 mixture is less than about 15° C.

[0120] In some embodiments, the agitating may comprise stirring at a stirring rates of about 50 revolutions per minute (rpm) to about 150 rpm. In some embodiments, the agitating may include stirring at a rate of at least about 50 rpm, 60 rpm, 70 rpm, 80 rpm, 90 rpm, 100 rpm, 110 rpm, 120 rpm, 130 rpm, 140 rpm, or 150 rpm. In some embodiments, the agitating may comprise stirring at a stirring rates of less than about 150 rpm. In some embodiments, the predetermined time for agitating the graphite oxidizing mixture is about 45 minutes to about 300 minutes. In some embodiments, the predetermined time for agitating the graphite oxidizing mixture is at least about 45 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes, 180 minutes, 200 minutes, 220 minutes, 240 minutes, 260 minutes, 280 minutes, or 300 minutes. In some embodiments, the predetermined time for agitating the graphite oxidizing mixture is at least between 45 minutes and 60 minutes, 60 minutes and 120 minutes, 120 minutes and 180 minutes, 180 minutes and 260 minutes, and 260 minutes and 300 minutes. In some embodiments, the predetermined time may or may not depend upon the stirring rate. In some embodiments, the predetermined time is independent of the stirring rate beyond a given threshold (e.g., a minimum stirring rate) and/or within a given range of stirring rates. In some embodiments, the reaction temperature of the graphite oxidizing mixture during the agitating is maintained below about 45° C. In some embodiments, the reaction temperature of the graphite oxidizing mixture during the agitating is maintained at less than or equal to about 15° C.

[0121] In some embodiments, cooling the graphite oxidizing mixture to the second predetermined temperature is achieved by quenching the graphite oxidizing mixture. In some embodiments, cooling the graphite oxidizing mixture to the second predetermined temperature is achieved by quenching the graphite oxidizing mixture with water, ice, a cooling coil, a coolant, or any combination thereof. In some embodiments, the second predetermined temperature is about 0° C. In some embodiments, the second predetermined temperature is about 0° C. to about 10° C. In some embodiments, the second predetermined temperature is greater than or equal to about 0° C. but less than or equal to about 1° C., 2° C., 3° C., 4° C., 5° C., 6° C., 7° C., 8° C., 9° C., or 10° C.

[0122] In some embodiments, the first reaction (oxidation) of the method provided herein for synthesizing a single-layer CBO or rCBO comprises: mixing graphene and sulfuric acid; chilling the solution; adding potassium permanganate powder; cooling the reaction; adding crushed ice to the reaction; stirring the solution; and quenching the reaction. In these embodiments, the graphite comprises 325sh natural flake graphite. In one example, about 32 L of 98% sulfuric acid and about 4.8 kg of potassium permanganate powder is used for every kilogram of graphite. In one example, the temperature of the solution is maintained by one or more cooling coils, wherein the reaction temperature is maintained at about −10° C. by setting the cooling coils' temperature to −2° C. In these embodiments, the potassium permanganate powder is adding over a period of about 1.5 hours, while maintaining a reaction temperature of below about 15° C. In one example, the temperature of the solution is maintained by one or more cooling coils, wherein the reaction temperature is allowed to heat up to about 20-30° C. over about 1.5 to about 2 hours by raising the reaction coil temperature to about 12° C. In one example, the temperature of the solution is maintained by one or more cooling coils, wherein the reaction temperature is further maintained at about 30° C. for approximately 30 minutes by cooling the reaction coils to about −2° C. In these embodiments, the about 32 kg of crushed ice is added to the reaction over the course of about 1 hour, wherein the reaction temperature climbs to about 50° C. In these embodiments, the solution is stirred or agitated for about 1 hour. In these embodiments, quenching the reaction is performed by adding about 72 kg of ice and/or 30% hydrogen peroxide (about 2 L) per kilogram of graphite, to stop and neutralize the reaction.

[0123] In some embodiments, the first reaction (oxidation) of the method provided herein to produce a multi-layer CBO or rCBO comprises: mixing graphene and sulfuric acid to form a solution; chilling the solution; adding potassium permanganate powder to the solution; stirring the solution and the potassium permanganate; and quenching the reaction. In this embodiment, the graphite is highly exfoliated, milled, small flake, large surface area, 9 micron flake sized, or any combination thereof. In these embodiments, about 25 L of 98% sulfuric acid and about 2 kg of potassium permanganate powder are used per kilogram of graphite. In one example, the temperature of the solution is maintained by one or more cooling coils, wherein the solution is chilled to a temperature of about −10° C. by setting the cooling coils to about −2° C. In one example, the potassium permanganate powder is adding over a period of about 45 minutes to about 1.5 hours to keep the reaction temperature below about 15° C. In these embodiment, the potassium permanganate, graphite, and sulfuric acid react for a period of time of about 30 minutes at reaction temperature of about 15° C. In these embodiments, the solution is stirred or agitated for about 30 minutes at a reaction temperature of about 15° C. In these embodiments, quenching the reaction is performed by adding about 125 kg of ice and/or 1 L of 30% hydrogen peroxide to stop and neutralize the reaction.

[0124] In some embodiments, the first purification step after the first reaction comprises a first filtration which removes impurities, such as sulfuric acid, manganese oxides, and manganese sulfate, and increases the pH of the solution to at least about 5. In some embodiments, the first purification step comprises rinsing the GO with water (e.g., deionized water), purifying the graphite oxide by chemistry dialysis, or a combination thereof (e.g., rinsing followed by dialysis). In some embodiments, the sulfuric acid concentration of the CBO after the first reaction is about 30% or about 60% for a single-layer or multi-layer CBO/rCBO, respectively, corresponding to a pH of approximately 0. In some embodiments, filtration is complete when the pH of the solution is about 5, corresponding to an acid concentration of about 0.00005%. In some embodiments, the first filtration comprises post-oxidation purification. In some embodiments, the concentration of GO in the solution after filtration is about 1% by mass (e.g., 1 kg GO in 100 L of aqueous solution).

[0125] In some embodiments, the CBO or rCBO is concentrated after purification to remove water and/or acid, to form a solution of, for example, 1% GO by weight. In some embodiments a given GO percentage by weight is required for certain applications, and to form dry powders and aqueous solutions.

[0126] In some embodiments, the reduction of CBO or GO to form rCBO or rGO, respectively, comprises a second reaction. In some embodiments, the second reaction comprises heating the CBO to about 90° C. and adding hydrogen peroxide over the course of about an hour. In some embodiments, the second reaction further comprises adding sodium ascorbate (e.g., C.sub.6H.sub.7NaO.sub.6) over the course of about 30 minutes to about 60 minutes. In one example, the second reaction uses about 1 L to about 2 L of 30% hydrogen peroxide, and about 5 kg of sodium ascorbate (sodium salt of ascorbic acid) per kg of GO in about 100 liters of. In some embodiments, the reaction continues to heat at about 90° C. for about 1.5 to about 3 more hours, before the addition of sodium ascorbate. In some embodiments, the reaction continues to heat at about 90° C. for a time period of about 1.5 hours, wherein the reaction occurs at a temperature of 90° C. for about 6 hours.

[0127] In some embodiments, the concentration of the GO by mass in the solution prior to the second reaction is about 0% to about 2% (e.g., 0-2 kg/100 L of aqueous solution). In some embodiments, the concentration of GO by mass is between about 0% and 0.5%, 0% and 1%, 0% and 1.5%, 0% and 2%, 0.5% and 1%, 0.5% and 1.5%, 0.5% and 2%, 1% and 1.5%, 1% and 2%, or 1.5% and 2%. In some embodiments, the concentration of GO by mass is less than about 2%, 1.5%, 1%, 0.5%, 0.25%, 0.1% or less. In some embodiments, the concentration of the GO is limited by the quantity of GO that may be dissolved in water while maintaining the fluidity required for manufacturing. In some embodiments, the solution becomes viscous at a concentration of 2% or more, (i.e., 2 kg or more of GO in 100 L of water). In some embodiments, a higher concentration (e.g., 1% by mass) reduces the required volume of water, which may decrease filtration time because the larger the volume of the solution, the longer the filtration process. In some embodiments, a quantity of water is filtered out at the end of the second reaction

[0128] In some embodiments, the volume 30% hydrogen peroxide per kilogram of GO is between about 10 L and 100 L, or between about 1 kg and 10 kg. In some embodiments, the volume of hydrogen peroxide per kilogram of GO (e.g., with a concentration of about 30% by weight) is between about 10 L and 20 L, 10 L and 30 L, 10 L and 40 L, 10 L and 50 L, 10 L and 60 L, 10 L and 70 L, 10 L and 80 L, 10 L and 90 L, 10 L and 100 L, 20 L and 30 L, 20 L and 40 L, 20 L and 50 L, 20 L and 60 L, 20 L and 70 L, 20 L and 80 L, 20 L and 90 L, 20 L and 100 L, 30 L and 40 L, 30 L and 50 L, 30 L and 60 L, 30 L and 70 L, 30 L and 80 L, 30 L and 90 L, 30 L and 100 L, 40 L and 50 L, 40 L and 60 L, 40 L and 70 L, 40 L and 80 L, 40 L and 90 L, 40 L and 100 L, 50 L and 60 L, 50 L and 70 L, 50 L and 80 L, 50 L and 90 L, 50 L and 100 L, 60 L and 70 L, 60 L and 80 L, 60 L and 90 L, 60 L and 100 L, 70 L and 80 L, 70 L and 90 L, 70 L and 100 L, 80 L and 90 L, 80 L and 100 L, or 90 L and 100 L. In some embodiments, the volume of hydrogen peroxide (e.g., with a concentration of about 30% by weight) per 1 kg GO is greater than or equal to about 10 L, 20 L, 30 L, 40 L, 50 L, 60 L, 70 L, 80 L, 90 L, or 100 L of hydrogen peroxide (e.g., with a concentration of about 30% by weight). In some embodiments, the volume of hydrogen peroxide (e.g., with a concentration of about 30% by weight) per 1 kg GO is less than about 100 L, 90 L, 80 L, 70 L, 60 L, 50 L, 40 L, 30 L, 20 L, or 15 L of hydrogen peroxide (e.g., with a concentration of about 30% by weight). In some embodiments, a volume of hydrogen peroxide equivalent to any of the aforementioned amounts of the 30% solution is added as a solution with a different concentration, or in concentrated or pure form (e.g., 90%-100% by weight). In some embodiments, the amount of hydrogen peroxide equivalent to any of the aforementioned amounts of the 30% solution is expressed in terms of volume based on a 100% (or pure) solution. In some embodiments, the amount of hydrogen peroxide equivalent to any of the aforementioned amounts of the 30% solution is expressed in terms of moles or in terms of weight of hydrogen peroxide (e.g., between about 3 kg (or 88 moles) and 30 kg (or 882 moles) of (pure) H.sub.2O.sub.2 is provided per 1 kg GO). In some embodiments, the amount of hydrogen peroxide equivalent to any of the aforementioned amounts of the 30% solution is expressed as a weight basis of pure hydrogen peroxide per 1 kg GO of between about 3 kg and 6 kg, 3 kg and 9 kg, 3 kg and 12 kg, 3 kg and 15 kg, 3 kg and 18 kg, 3 kg and 21 kg, 3 kg and 24 kg, 3 kg and 27 kg, 3 kg and 30 kg, 6 kg and 9 kg, 6 kg and 12 kg, 6 kg and 15 kg, 6 kg and 18 kg, 6 kg and 21 kg, 6 kg and 24 kg, 6 kg and 27 kg, 6 kg and 30 kg, 9 kg and 12 kg, 9 kg and 15 kg, 9 kg and 18 kg, 9 kg and 21 kg, 9 kg and 24 kg, 9 kg and 30 kg, 12 kg and 15 kg, 12 kg and 18 kg, 12 kg and 21 kg, 12 kg and 24 kg, 12 kg and 27 kg, 12 kg and 30 kg, 15 kg and 18 kg, 15 kg and 21 kg, 15 kg and 24 kg, 15 kg and 30 kg, 18 kg and 21 kg, 18 kg and 24 kg, 18 kg and 27 kg, 18 kg and 30 kg, 21 kg and 24 kg, 21 kg and 27 kg, 21 kg and 30 kg, 24 kg and 27 kg, 24 kg and 30 kg, or 27 kg and 30 kg. In some embodiments, the amount of pure hydrogen peroxide per 1 kg GO equivalent to any of the aforementioned amounts of the 30% solution is expressed as a weight basis, greater than or equal to about 3 kg, 6 kg, 9 kg, 12 kg, 15 kg, 18 kg, 21 kg, 24 kg, or 30 kg. In some embodiments, the amount of pure hydrogen peroxide per 1 kg GO equivalent to any of the aforementioned amounts of the 30% solution is expressed as a weight basis as less than about 30 kg, 24 kg, 21 kg, 18 kg, 15 kg, 12 kg, 9 kg, 6 kg, or 4.5 kg.

[0129] In some embodiments, the mass of sodium ascorbate per 1 kg of GO is between about 1 kg and 10 kg, between about 1 kg and 2 kg, 1 kg and 3 kg, 1 kg and 4 kg, 1 kg and 5 kg, 1 kg and 6 kg, 1 kg and 7 kg, 1 kg and 8 kg, 1 kg and 9 kg, 1 kg and 10 kg, 2 kg and 3 kg, 2 kg and 4 kg, 2 kg and 5 kg, 2 kg and 6 kg, 2 kg and 7 kg, 2 kg and 8 kg, 2 kg and 9 kg, 2 kg and 10 kg, 3 kg and 4 kg, 3 kg and 5 kg, 3 kg and 6 kg, 3 kg and 7 kg, 3 kg and 8 kg, 3 kg and 9 kg, 3 kg and 10 kg, 4 kg and 5 kg, 4 kg and 6 kg, 4 kg and 7 kg, 4 kg and 8 kg, 4 kg and 9 kg, 4 kg and 10 kg, 5 kg and 6 kg, 5 kg and 7 kg, 5 kg and 8 kg, 5 kg and 9 kg, 5 kg and 10 kg, 6 kg and 7 kg, 6 kg and 8 kg, 6 kg and 9 kg, 6 kg and 10 kg, 7 kg and 8 kg, 7 kg and 9 kg, 7 kg and 10 kg, 8 kg and 9 kg, 8 kg and 10 kg, or 9 kg and 10 kg. In some embodiments, the mass of sodium ascorbate per 1 kg GO is greater than or equal to about 1 kg, 2 kg, 3 kg, 4 kg, 5 kg, 6 kg, 7 kg, 8 kg, 9 kg, or 10 kg. In some embodiments, the mass of sodium ascorbate per 1 kg GO is less than about 15 kg, 14 kg, 13 kg, 12 kg, 11 kg, 10 kg, 9 kg, 8 kg, 7 kg, 6 kg, 5 kg, 4 kg, 3 kg, 2 kg, or 1.5 kg.

[0130] In some embodiments, the reaction temperature during the second reaction is about 60° C. to about 180° C. In some embodiments, the reaction temperature during the second reaction comprises at a variety of temperatures or a constant temperature. In some embodiments, the reaction temperature during the second reaction is between about 60° C. and 80° C., 60° C. and 90° C., 60° C. and 100° C., 60° C. and 120° C., 60° C. and 140° C., 60° C. and 160° C., 60° C. and 180° C., 80° C. and 90° C., 80° C. and 100° C., 80° C. and 120° C., 80° C. and 140° C., 80° C. and 160° C., 80° C. and 180° C., 90° C. and 100° C., 90° C. and 120° C., 90° C. and 140° C., 90° C. and 160° C., 90° C. and 180° C., 100° C. and 120° C., 100° C. and 140° C., 100° C. and 160° C., 100° C. and 180° C., 120° C. and 140° C., 120° C. and 160° C., 120° C. and 180° C., 140° C. and 160° C., 140° C. and 180° C., or 160° C. and 180° C. In some embodiments, the reaction temperature during the second reaction is or is not allowed to change or fluctuate within a given range (e.g., the temperature for a given step is kept constant at a given temperature within a given range or may fluctuate within the given range). In some embodiments, (e.g., at temperatures above about 100° C.), the reaction chamber is sealed.

[0131] In some embodiments, a percentage of the GO that is converted (hereafter referred to as “y”) is at least about 90%, 95%, 98%, 99%, 99.5%, or 100%. In some embodiments, between 90% and 95% by weight of the GO is converted. In other embodiments, between 95% and 95.5% by weight of the GO is converted. In some embodiments, the amount of rGO produced per unit of GO depends on the oxygen content of the GO and the rGO. In some embodiments, the C:O atomic ratio of the GO is between about 4:1 and 5:1, and the oxygen content of the rGO is less than or equal to about 5 atomic percent. In some embodiments, the weight of rGO produced per kilogram of GO is between about 0.75y kilograms and 0.84 kilograms. In some embodiments, the C:O atomic ratio of the GO is between about 7:3 and 5:1, wherein the oxygen content of the rGO is less than or equal to about 5 atomic percent. In some embodiments, the amount of rGO produced per mass unit of GO is between about 0.64y and 0.84. In some embodiments, the C:O atomic ratio of the GO is at least about 7:3, wherein the oxygen content of the rGO is less than or equal to about 5 atomic percent. In some embodiments, the amount of rGO produced per mass unit of GO is at least about 0.64y. In some embodiments, the amount of rGO produced per mass unit of GO is at least about 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, or 0.8. In some embodiments, the amount of rGO produced per mass unit of GO is between about 0.5 and 0.85, 0.6 and 0.8, or 0.7 and 0.8 units of rGO.

[0132] In some embodiments, the second reaction is performed separately from the first reaction. For example, the second reaction followed by a second filtration, may be performed using any graphite oxide feedstock with suitable specifications.

[0133] In some embodiments, a second filtration or purification is performed after the second reaction to remove such impurities as, for example, sodium ascorbate, sulfuric acid, manganese oxides, and manganese salts and other salts.

[0134] In some embodiments, the purification comprises washing the rGO solution with de-ionized (DI) water (e.g., with copious amounts of DI water) until the conductivity of the rGO solution reaches about 50 microsiemens per centimeter (0/cm) or less. In some embodiments, the rGO solution contains about 4.95 kg of sodium ascorbate per kg of rGO and has a conductivity of greater than about 200 mS/cm. In some embodiments, for some uses a specific concentration may be required for some processes that use rGO, such as about 2% by weight or greater.

[0135] In some embodiments, the purification comprises tangential flow filtering until the product has a pH of about 5. In some embodiments, the filter is a modified polyether sulfone hollow filter membrane with about 0.02 micron pore size. The purified GO may then be concentrated to a solution of about 1% by weight.

[0136] In some embodiments, purification comprises vacuum filtration through, for example, a 2 micron 316 stainless steel mesh filter, wherein water is flushed through the rGO to remove all salts. In some embodiments, Purification is complete when the rGO solution has a conductivity of about 50 μS/cm or less.

[0137] In some embodiments, the mixing speed or stirring rate (e.g., during one or more reaction processes) is about 200 rpm. In some embodiments, the mixing speed is at least about 100 rpm, 110 rpm, 120 rpm, 130 rpm, 140 rpm, 150 rpm, 160 rpm, 170 rpm, 180 rpm, 190 rpm, or 200 rpm. In some embodiments, the mixing speed is between about 100 rpm and about 150 rpm. In another embodiment, the mixing speed is between about 150 rpm and about 200 rpm.

[0138] In some embodiments, product synthesized when the first and second reactions are performed below ambient reaction temperature show improved capacitance, wherein the methods thereby are safer and more controlled. In some embodiments, an ambient reaction temperature comprises a reaction performed in room temperature surroundings without external cooling. The reaction conditions include Rainbow Reactions (RR) that are time variable reactions so named due to a spectrum of colors produced during synthesis. In some embodiments, a first Rainbow Reaction RR 1, a second Rainbow Reaction RR 2, and a third Rainbow reaction RR 3, or any combination thereof, per FIG. 2, comprise ambient reactions. In some embodiments, below ambient reactions further increase product performance and method stability and accuracy.

[0139] In one example a method for synthesizing a CBO or rCBO material, per FIG. 2, comprises the following time variable RRs: [0140] RR 1) Forming a solution of graphite and concentrated sulfuric acid at about 0° C. using ice bath or cooling coils. [0141] RR 2) Adding KMnO.sub.4 (exothermic) while maintain a reaction temperature of below about 15° C. using an ice bath or cooling coils. [0142] RR 3) Stirring the reaction for about 45 minutes. [0143] RR 4) Quenching the reaction by adding ice and/or 30% H.sub.2O.sub.2 to the reaction mixture. [0144] RR 5) Purifying the graphite oxide with one or more H.sub.2O washes, followed by about 1 week of continuous-flow dialysis.

[0145] In one example, the mass of the graphite is about 15 g, the volume of the concentrated sulfuric acid is about 750 mL, the mass of the KMnO.sub.4 is about 90 g, the mass of ice is at least about 2.6 g, and the volume of H.sub.2O.sub.2 is at least about 75 mL. In some embodiments, the graphite is provided in powder form. In an example, the total processing time is about 1 week, and the total cost is about $21/kg of GO or rGO.

[0146] In some embodiments, the amount of oxidizing agent (also “oxidizer” herein) may be provided in terms of a ratio of oxidizing agent (KMnO.sub.4) to graphite (also “Ox:Gr” herein). In one example, about 90 g KMnO.sub.4 is used per 15 g graphite, corresponding to about 6× mass ratio Ox:Gr. In another example, about 75 mL 30% H.sub.2O.sub.2 (e.g., about 30% by weight in aqueous solution, corresponding to about 0.66 moles H.sub.2O.sub.2) is used (i) per 90 g KMnO.sub.4, corresponding to about 0.25 units of H.sub.2O.sub.2 per unit of KMnO.sub.4 on a weight basis or about 1.16 units of H.sub.2O.sub.2 per unit of KMnO.sub.4 on a molar basis, or (ii) per 750 mL concentrated sulfuric acid with a concentration of between about 96% H.sub.2SO.sub.4 and 98% H.sub.2SO.sub.4 (e.g., by weight in aqueous solution), corresponding to a volume ratio of 30% H.sub.2O.sub.2 to concentrated sulfuric acid of about 10:1 (e.g., about 1 liter of aqueous solution having about 30% H.sub.2O.sub.2 for every 10 liters of concentrated H.sub.2SO.sub.4). In yet another example, about 50 liters of concentrated H.sub.2SO.sub.4 is consumed for every 1 kilogram of graphite. Further examples of amounts and ratios are provided elsewhere herein, for example, in relation to methods for producing single-layer GO and multi-layer GO (e.g., on a per kilogram graphite oxide basis).

[0147] In some embodiments, the stirring time may vary, wherein the 45 minutes was selected based on the best measured sample. In some embodiments, the reaction temperature may vary with time according to specific cooling conditions (e.g., presence or absence of cooling by ice bath or cooling coils).

[0148] In some embodiments, RR 5 comprises at least 1, 2, 3, 4, 5 (e.g., 5) or more water washes. In some embodiments, the purification further comprises additional water purification processes, such as, for example, dialysis. In some embodiments, dialysis comprises placing the material in a porous tube and removing (e.g., leaching out) ions from the material through the walls of the tube into a water bath that is refreshed continuously or batch-wise. In some embodiments, the method comprises or further comprises one or more filtration methods other than dialysis (e.g., after the H.sub.2O washes, another filtration method may be applied in lieu of dialysis). In one example, the filtration process takes less than about 1 week, wherein the duration of the filtration may depend on batch size. For example, for a 15 g graphite batch, per above, filtration may take less than or equal to about 1 or 2 days. In one example, total filtration (e.g., dialysis) time may be less than or equal to about 7 days, 6 days, 5 days, 4 days, 3 days, 2 days, 1 day, or ½ day. In some embodiments, a shorter filtration time may reduce the total processing time to less than or equal to about 7 days, 6 days, 5 days, 4 days, 3 days, 2 days, 1 day, or ½ day.

[0149] In some embodiments, all of the graphite is converted to a CBO or an rCBO material. In some embodiments, the quantity of the CBO or the rCBO material that is produced per unit of graphite depends on the oxygen content of the CBO and the rCBO materials. In some embodiments, the weight of the CBO or rCBO materials produced is greater than the weight of the consumed graphene by a factor of about 1 to about 3 (e.g., 1.27 or 1.33). In some embodiments, the C:O atomic ratio of the CBO or the rCBO material is about 4:1 and 5:1, wherein the C:O atomic ratio of the GO may differ for single-layer and multi-layer CBO and the rCBO materials (e.g., as described in relation to FIG. 9). Thus, in some embodiments the amount of GO produced per unit of graphite may differ for single-layer and multi-layer CBO or rCBO.

[0150] In some embodiments, the concentration of one or more of the reactants varies. In an example, the concentration of the sulfuric acid is between about 96% and 98% by weight in aqueous solution. In some embodiments the quantity of H.sub.2O.sub.2 may be represented as a ratio between the mass of the H.sub.2O.sub.2 and the mass of the KMnO.sub.4, which may affect the quantity of the manganese species within the CBO or rCBO. In other embodiments, the concentrations and quantities of the reactants may be represented by molar amounts. In some embodiments, employing concentrations of sulfuric acid below about 96% (e.g., by weight in aqueous solution) may alter the morphology of the CBO or rCBO, and/or reduce the concentration of oxygen-containing groups.

[0151] FIGS. 3, 4, 5, and 8 show characteristics of the CBO and rCBO. Per FIG. 3, as the RR 1 reaction is self-heated (exothermic), extended RR 1 reactions at higher temperatures synthesize CBO and rCBO materials with lower capacitances. Per FIG. 3, the capacitance of exemplary CBO and rCBO products are compared to their reaction temperature as functions of reaction time (in hours) at a scan rate of 10 millivolts per second (mV/s).

[0152] In one example, it was determined that the greatest capacitance at 10 mV/s and at 20 min of 49 mF/cm.sup.2 occurs with a 6× Ox:Gr mass ratio and a reaction time of 0-20 hours. In this example, the peak capacitance for RR 1 was measured for an ICCN formed by light-scribing the GO produced by the method of FIG. 2. In some embodiments, the peak capacitance for RR 1 of the unreduced GO is about the same as for the rGO (ICCN).

[0153] In some embodiments, per FIG. 4, shorter RR 2 reaction times led to higher capacitances, by retaining a more pristine sp2 structure of graphene with less oxidative damage. In some embodiments, the term sp2 is a hybridization of s, px, and py atomic orbitals to form a trigonal planar molecular configuration with 120 degree angles. In some embodiments, the optimal RR2 reaction occurred with a 6× mass ratio Ox:Gr, over 0-2 hours, which yielded a peak capacitance at about 10 mV/s and at about 15 minutes of about 87 mF/cm.sup.2. In this example, the peak capacitance for RR 2 was measured for an ICCN formed by light-scribing the GO produced by the method of FIG. 2 with process #3 corresponding to RR 2. The peak capacitance for RR 2 of the unreduced GO is about the same as for the rGO (ICCN).

[0154] In some embodiments, colder reaction temperatures in RR 3, per FIG. 5, enabled a greater window of opportunity to quench the reaction at the right time. In some embodiments, the optimal RR3 reaction occurred with a 6× mass ratio Ox:Gr, and a reaction time to yield a product with a peak capacitance in about 10 mV/s at about 45 min of about 459 mF/cm.sup.2. In this example, the peak capacitance for RR 3 was measured for an ICCN formed by light-scribing the GO produced by the method of FIG. 2 with step 3 corresponding to RR 2. The peak capacitance for RR 3 of the unreduced GO is about the same as for the rGO (ICCN).

[0155] In some embodiments, per FIG. 8, the use or the number of HCl washes in RR 5 may not have a significant effect on the capacitance of the CGO or the rCGO, whereas a capacitance variation of about 11% among the number of wash cycles, with no visible trend, was observed.

[0156] In some embodiments, optimal RR 5 conditions comprise a 6× mass ratio Ox:Gr, ice bath cooling for 0-1 hour with or without the use of one or more HCl washes, which achieved a peak capacitance at about 10 mV/s and about 31 min of about 261 mF/cm.sup.2. In this example, the peak capacitance for RR 5 was measured for an ICCN formed by light-scribing the GO produced by a modified version of the method in FIG. 2. In some embodiments, the peak capacitance for RR 5 of the unreduced GO is about the same as for the rGO (ICCN).

[0157] In some embodiments, removal of HCl from the purification steps shows no loss of capacitance and significantly reduces the cost of the product, while expediting the purification procedure. Removal of HCl from the purification steps may provide one or more (any combination, or all) of the aforementioned advantages.

Carbon-Based Oxide or Reduced Carbon-Based Oxide Materials

[0158] Any aspects of the disclosure described in relation to graphene may equally apply to rGO (e.g., ICCN, or porous carbon sheet(s)) at least in some configurations, and vice versa. The rGO (e.g., graphene or ICCN) may be treated. In some embodiments, the rGO (e.g., ICCN) comprises a two-dimensional (2-D) material (e.g., porous carbon sheet(s)) or a three-dimensional (3-D) material (e.g., ICCN). In some embodiments, primarily two-dimensional or three-dimensional materials may be desirable for different applications and uses.

[0159] In some embodiments, an ICCN comprises a plurality of expanded and interconnected carbon layers, wherein the term “expanded,” refers to a plurality of carbon layers that are expanded apart from one another, means that a portion of adjacent ones of the carbon layers are separated by at least about 2 nanometers (nm). In some embodiments, at least a portion of adjacent carbon layers are separated by greater than or equal to about 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, or 100 nm. In some embodiments, at least a portion of adjacent carbon layers are separated by less than about 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, or 100 nm. In some embodiments, at least a portion of adjacent carbon layers are separated by between about 2 nm and 10 nm, 2 nm and 25 nm, 2 nm and 50 nm, or 2 nm and 100 nm. In some embodiments, the plurality of carbon layers has an electrical conductivity greater than about 0.1 siemens per meter (S/m). In some embodiments, each of the plurality of carbon layers is a two-dimensional material with only one carbon atom of thickness. In some embodiments, each of the expanded and interconnected carbon layers may comprise at least one, or a plurality of corrugated carbon sheets that are each one atom thick.

[0160] FIG. 9 is an exemplary illustration of various carbon forms 905, 910, 915, 920, and 925, which may or may not comprise functional groups, and may be employed to synthesize an array of carbon-based materials. In some embodiments, a given carbon form comprises one or more hydroxyl and/or epoxy functional groups 930, one or more carboxylic functional groups 935, one or more other functional groups (e.g., carbonyl functional groups), or any combination thereof.

[0161] In some embodiments, the carbon form comprises graphite 905, wherein the graphite comprises a plurality of carbon sheets 940 (e.g., greater than or equal to about 100, 1,000, 10,000, 100,000, 1 million, 10 million, 100 million, or more) that are each one atom thick. In some embodiments, the plurality of carbon sheets 940 are stacked on top of each other and stick together due to van der Waals interactions, such that the interior of the stack is not accessible (e.g., only top and bottom sheets are accessible). In some embodiments, the carbon form 910 comprises graphene, which comprises a carbon sheet 945 that is one atom thick, and may comprise functional groups. In some embodiments, the carbon form 915 comprises graphene oxide (e.g., singular graphite oxide in solution), which comprises a carbon sheet 950 that is one atom thick.

[0162] In some embodiments, one or more carbon forms 915 may agglomerate, wherein individual carbon sheets 960 are separated, or may remain separated due to van der Waals interactions. In some embodiments, the carbon form 915 includes one or more hydroxyl and/or epoxy functional groups 930, and one or more carboxylic functional groups 935, wherein the hydroxyl and/or epoxy functional groups 930 are attached or otherwise associated with/bonded to the surfaces of the carbon sheet 950. In some embodiments, the carboxylic functional groups 935 is attached or otherwise associated with or bonded to the edges of the carbon sheet 950.

[0163] In some embodiments, the carbon form 920 comprises reduced graphene oxide (e.g., PCS formed in solution), comprising a carbon sheet 955 that is one atom thick. In some embodiments, the carbon form 920 comprises one or more carboxylic functional groups 935 which are attached or otherwise associated with or bonded to the edges of the carbon sheet 955.

[0164] In some embodiments, the carbon form 925 comprises two or more layers of graphene oxide (e.g., bilayer or trilayer graphite oxide in solution), wherein each carbon sheet or layer 960 is one atom thick, and wherein the two or more carbon sheets or layers 960 are held together by van der Waals interactions. In some embodiments, the number layer graphene oxide is greater than or equal to 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon sheets or layers 960 In some embodiments, the number layer graphene oxide is less than or equal to 10 carbon sheets or layers 960 (e.g., up to 10 carbon sheets or layers). In some embodiments, the number layer graphene oxide is between 2 and 3, 2 and 4, 2 and 5, 2 and 6, 2 and 7, 2 and 8, 2 and 9, 2 and 10, 3 and 4, 3 and 5, 3 and 6, 3 and 7, 3 and 8, 3 and 9, 3 and 10, 4 and 5, 4 and 6, 4 and 7, 4 and 8, 4 and 9, 4 and 10, 5 and 6, 5 and 7, 5 and 8, 5 and 9, 5 and 10, 6 and 7, 6 and 8, 6 and 9, 6 and 10, 7 and 8, 7 and 9, 7 and 10, 8 and 9, 8 and 10, or 9 and 10 carbon sheets or layers 960. In some embodiments, the number layer graphene oxide is 2 and 4, or 2 and 3 carbon sheets or layers 960. In some embodiments, the number layer graphene oxide is up to 4 carbon sheets or layers 960 In some embodiments, the number layer graphene oxide is 4 carbon sheets or layers 960.

[0165] In some embodiments, the carbon form 925 includes one or more carboxylic functional groups 935, wherein the carboxylic functional groups 935 are attached or otherwise associated with or bonded to edges of the one or more of the carbon sheets or layers 960. In some embodiments, the carboxylic functional groups 935 are primarily attached or bonded to the edges of the top and bottom carbon sheets or layers 960 in a stack of the carbon sheets or layers 960. In some embodiments, the carboxylic functional groups 935 may be attached to or otherwise associated with/bonded to edges of any (e.g., each, or at least 2, 3, 4, or more) of the carbon sheets or layers 960.

[0166] In some embodiments, the presence and quantity of functional groups impacts the overall carbon to oxygen (C:O) atomic ratio of the carbon forms seen in FIG. 9. For example, the carbon forms 925 and 915 may differ in the amount and/or type of oxygen functionality. In another example, the carbon form 925 may be produced upon oxidation of the carbon form 905, and the carbon form 925 may in turn be further oxidized to the carbon form 915. In some embodiments, each of the carbon forms in FIG. 9 may be produced via one or more pathways, and/or at least some of the carbon forms in FIG. 9 may be transformed between one another at least in some implementations. For example, the carbon form 915 may be formed via an alternative pathway.

[0167] FIG. 10 schematically illustrates an example of another carbon form 1000 comprising reduced graphite oxide. In some embodiments, the carbon form 1000 comprises an interconnected corrugated carbon-based network (ICCN) comprising a plurality of expanded and interconnected carbon layers 1005 that are interconnected and expanded apart from one another to form a plurality of pores 1010. FIG. 10 illustrates a cross-section of an exemplary ICCN that results from deoxygenating an rCBO.

[0168] FIG. 11 schematically illustrates an example of yet another carbon form 1100 of reduced graphite oxide comprising an interconnected corrugated carbon-based network (ICCN) made up of a plurality of expanded and interconnected carbon layers that include corrugated carbon layers such as a single corrugated carbon sheet 1105. In some embodiments, each of the expanded and interconnected carbon layers comprises at least one corrugated carbon sheet that is one atom thick. In another embodiment, each of the expanded and interconnected carbon layers comprise a plurality of corrugated carbon sheets that are each one atom thick. In some embodiments, a single-layer GO comprises between about 93% and 96% (e.g., by weight) of singular graphene oxide (e.g., carbon form 915 in FIG. 9). In some embodiments, a multi-layer GO comprises a given distribution (e.g., by weight) of number of layers (e.g., a distribution of carbon forms 925 with different numbers of layers). For example, a multi-layer GO may comprise greater than or equal to about 5%, 10%, 15%, 25%, 50%, 75%, 85%, 90%, or 95% (e.g., by weight) of a carbon form 925 with a given number of layers (e.g., 3 or 4). In other example, the multi-layer GO comprises a carbon form 925 by weight of between 5% and 25%, 25% and 50%, 50% and 75%, and 75% and 95% with a given number of layers. In some embodiments, the multi-layer GO comprises a percentages of a carbon form 925 together with less than or equal to about 95%, 90%, 75%, 50%, 25%, 15%, 10%, or 5% (e.g., by weight) of another carbon form 925 with a different number of layers. In some embodiments, a multi-layer GO may comprise less than about 95%, 90%, 85%, 75%, 50%, 25%, 15%, 10%, or 5% (e.g., by weight) of a carbon form 925 with a given number of layers. In some embodiments, the rGO comprises substantially sp2 carbon, substantially non-sp2 carbon, or a mixture of sp2 carbon and non-sp2 carbon.

[0169] In some embodiments, the CBO and/or the rCBO materials synthesized by a method of the present disclosure exhibit a specific or minimum purity or grade. In some embodiments, the purity or grade of a CBO or an rCBO (e.g., graphite oxide) is provided in terms of post-purification ionic conductivity.

[0170] In addition, the methods provide herein allow for adjustability of the electrical conductivity, the number of layers of graphene oxide sheets, and the degree of oxidation of the CBO or the rCBO. In some embodiments, reaction conditions may be adjusted to synthesize two forms of CBO comprising single-layer graphite oxide or multi-layer graphite oxide, wherein each form exhibits unique physicochemical properties and/or performance characteristics such as conductivity or purity.

[0171] Graphite oxide may be used as a feedstock for production of graphene, an interconnected corrugated carbon-based network (ICCN), wherein each ICCN comprises a plurality of expanded and interconnected carbon layers, porous carbon sheets (PCS), or other materials derived from graphite oxide reduced forms of graphite oxide (rGO) may comprise three-dimensional (e.g., ICCN) forms of carbon, two-dimensional (e.g., porous carbon sheet) forms of carbon, or a combination thereof (e.g., a material comprising both two- and three-dimensional forms of carbon). In some embodiments, the rGO is porous.

[0172] In some embodiments, the CBO and rCBO materials produced by the methods of the present disclosure exhibit a consistent, repeatable degree of oxygen functionality, oxidation and exfoliation, which limits water absorption to allow the CBO and rCBO materials to be effectively light-scribed (e.g., laser-scribed). In some embodiments, a CBO (e.g., graphite oxide) that is not properly oxidized and exfoliated absorbs too much water, the water may absorb a substantial amount of energy to inhibit the CBO's ability to be effectively light-scribed (e.g., laser-scribed), For example, an over-oxidized graphite oxide may comprise an excessive amount and/or unsuitable types of oxygen functionality that allow an excessive amount of water to be absorbed.

[0173] In some embodiments, an ICCN is produced from light-scribing (e.g., laser-scribing) carbon-based films such as those formed of graphite oxide. In some embodiments, rGO produces a highly conductive and high surface area laser-scribed graphene (LSG) framework that is a form of ICCN. In some embodiments, forming an ICCN (e.g., a porous ICCN) comprises disposing a solution comprising CBO and a liquid onto a substrate, evaporating the liquid from the solution to form the film, and exposing the film to light. In some embodiments, the light source comprises a laser, a flash lamp, or other high intensity light sources, wherein the light has an intensity of about 5 milliwatts to about 350 milliwatts. In some embodiments, the GO produced by the method disclosed herein is not light-scribed.

[0174] In some embodiments, the ICCN comprises an expanded interconnected network of carbon layers, and exhibits a high surface area and electrical conductivity. In some embodiments, the ICCN has a surface area of greater than or equal to about 500 square meters per gram (m.sup.2/g), 1000 m.sup.2/g, 1400 m.sup.2/g, 1500 m.sup.2/g, 1750 m.sup.2/g, or 2000 m.sup.2/g. In some embodiments, the ICCN has a surface area of between about 100 m.sup.2/g and 1500 m.sup.2/g, 500 m.sup.2/g and 2000 m.sup.2/g, 1000 m.sup.2/g and 2500 m.sup.2/g, or 1500 m.sup.2/g and 2000 m.sup.2/g. In some embodiments, the ICCN exhibits an electrical conductivity of greater than or equal to about 1500 S/m, 1600 S/m, 1650 S/m, 1700 S/m, 1750 S/m, 1800 S/m, 1900 S/m, or 2000 S/m. In one embodiment, the ICCN exhibits an electrical conductivity of greater than about 1700 S/m and a surface area that is greater than about 1500 m.sup.2/g. In another embodiment, the ICCN exhibits an electrical conductivity of about 1650 S/m and a surface area of about 1520 m.sup.2/g. In some embodiments, the reduction of GO forms rGO, wherein the rGO exhibits a higher conductivity that is more suitable for light-scribing.

[0175] In some embodiments, the ICCN has a very low oxygen content of only 3.5%. In some embodiments, the oxygen content of the ICCN ranges between about 1% and 5%, 1% and 4%, 1% and 3%, 1% and 2%, 0% and 1%, 0% and 2%, 0% and 3%, 0% and 4%, 0% and 5%, 2% and 3%, 2% and 4%, 2% and 5%, 3% and 4%, 3% and 5%, or 4% and 5%. In some embodiments, an ICCN may have an oxygen content of less than or equal to about 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, or 0.5%. In some embodiments, the oxygen contents is measured by X-ray photoelectron spectroscopy (XPS) (e.g., in atomic percent). In some embodiments, the ICCN exhibits a low oxygen content, a high surface area, and a suitable (e.g., not too high and not too low) electrical conductivity, including any combination of the aforementioned oxygen contents, surface areas, and electrical conductivities.

[0176] In some embodiments, one or more porous carbon sheets (PCS) may be formed from GO or rGO. In some embodiments, the rGO is dispersible in a variety of solutions. In some embodiments, PCS is formed by through chemical reduction in solution. In some embodiments, the PCS has an oxygen content of less than or equal to about 10%, 9%, 8%, 7%, 6%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, or 0.5%. In some embodiments, the PCS has a pore size of less than or equal to about 10 nanometers (nm), 9 nm, 8 nm, 7 nm, 6 nm, 5 nm, 4 nm, 3 nm, 2 nm, or 1 nm. In some embodiments, the PCS has a pore size of greater than or equal to about 1 nm. In some embodiments, the PCS has a pore size of between about 1 nm and 2 nm, 1 nm and 3 nm, 1 nm and 4 nm, 1 nm and 5 nm, 1 nm and 6 nm, 1 nm and 7 nm, 1 nm and 8 nm, 1 nm and 9 nm, 1 nm and 10 nm, 2 nm and 3 nm, 2 nm and 4 nm, 2 nm and 5 nm, 2 nm and 6 nm, 2 nm and 7 nm, 2 nm and 8 nm, 2 nm and 9 nm, 2 nm and 10 nm, 3 nm and 4 nm, 3 nm and 5 nm, 3 nm and 6 nm, 3 nm and 7 nm, 3 nm and 8 nm, 3 nm and 9 nm, 3 nm and 10 nm, 4 nm and 5 nm, 4 nm and 6 nm, 4 nm and 7 nm, 4 nm and 8 nm, 4 nm and 9 nm, 4 nm and 10 nm, 4 nm and 5 nm, 4 nm and 6 nm, 4 nm and 7 nm, 4 nm and 8 nm, 4 nm and 9 nm, 5 nm and 10 nm, 6 nm and 7 nm, 6 nm and 8 nm, 6 nm and 9 nm, 6 nm and 10 nm, 7 nm and 8 nm, 7 nm and 9 nm, 7 nm and 10 nm, 8 nm and 9 nm, 8 nm and 10 nm, or 9 nm and 10 nm. In some embodiments, the PCS has a pore size between about 1 nm and 4 nm, or 1 nm and 10 nm. The PCS may have one or more pore sizes (e.g., the PCS may have a distribution of such pore sizes).

[0177] In some embodiments, the GO may not need to be reduced, wherein the capacitance and/or conductivity of the unreduced GO may be substantially the same as that of the rGO (e.g., ICCN) because in some instances only the edges of the graphite are oxidized while the internal material maintains a large portion of the conductive properties of graphene (e.g., see carbon form 925 in FIG. 9). In some embodiments, GO and rGO produced by the methods herein may exhibit a similar degree of oxidation when oxidized (e.g., from the carbon form 905) to the carbon form 925. In some embodiments, the GO's properties are substantially the same as or similar to rGO produced from one or more of the oxidized carbon forms in FIG. 9 (e.g., substantially the same as or similar to rGO produced from the carbon form 925). In other embodiments, the conductivity of the GO or the rGO is between 0.1 S/m and 0.5 S/m, 0.5 S/m and 1 S/m, 1 S/m and 10 S/m, 10 S/m and 100 S/m, 100 S/m and 500 S/m, 500 S/m and 1000 S/m, 1000 S/m and 1700 S/m.

[0178] In some embodiments, further oxidation of GO alters its properties, wherein for example, further oxidizing the carbon form 925 to the carbon form 915, forms a product that is dissimilar from an rGO. For example, a device per FIG. 7A comprising a GO oxidized to the carbon form 925 (e.g., comprising a few layer graphene oxide having 3 to 5 carbon sheets or layers 960) may have substantially the same performance as the device in FIG. 7A. However, for example, the same device may or may not have substantially the same performance as the device in FIG. 7A when further oxidized to the carbon form 915.

[0179] In some embodiments, a double-layer device comprising at least one electrode comprising an unreduced or a reduced GO formed by the method provided herein has a capacitance (e.g., a peak capacitance) of greater than or equal to about 1 mF/cm.sup.2, 2 mF/cm.sup.2, 3 mF/cm.sup.2, 4 mF/cm.sup.2, 5 mF/cm.sup.2, 6 mF/cm.sup.2, 7 mF/cm.sup.2, 8 mF/cm.sup.2, 9 mF/cm.sup.2, 10 mF/cm.sup.2, 15 mF/cm.sup.2, 20 mF/cm.sup.2, 25 mF/cm.sup.2, 30 mF/cm.sup.2, 40 mF/cm.sup.2, 50 mF/cm.sup.2, 60 mF/cm.sup.2, 70 mF/cm.sup.2, 80 mF/cm.sup.2, 90 mF/cm.sup.2, 100 mF/cm.sup.2, 110 mF/cm.sup.2, 120 mF/cm.sup.2, 130 mF/cm.sup.2, 140 mF/cm.sup.2, 150 mF/cm.sup.2, 160 mF/cm.sup.2, 170 mF/cm.sup.2, 180 mF/cm.sup.2, 190 mF/cm.sup.2, 200 mF/cm.sup.2, 210 mF/cm.sup.2, 220 mF/cm.sup.2, 230 mF/cm.sup.2, 240 mF/cm.sup.2, 250 mF/cm.sup.2, 260 mF/cm.sup.2, 270 mF/cm.sup.2, 280 mF/cm.sup.2, 290 mF/cm.sup.2, 300 mF/cm.sup.2, 310 mF/cm.sup.2, 320 mF/cm.sup.2, 330 mF/cm.sup.2, 340 mF/cm.sup.2, 350 mF/cm.sup.2, 360 mF/cm.sup.2, 370 mF/cm.sup.2, 380 mF/cm.sup.2, 390 mF/cm.sup.2, 400 mF/cm.sup.2, 410 mF/cm.sup.2, 420 mF/cm.sup.2, 430 mF/cm.sup.2, 440 mF/cm.sup.2, 450 mF/cm.sup.2, 460 mF/cm.sup.2, 470 mF/cm.sup.2, 480 mF/cm.sup.2, 490 mF/cm.sup.2, 500 mF/cm.sup.2, 550 mF/cm.sup.2, 600 mF/cm.sup.2, 650 mF/cm.sup.2, 700 mF/cm.sup.2, 750 mF/cm.sup.2, 800 mF/cm.sup.2, or more. In some embodiments, a double-layer device comprising at least one electrode comprising the unreduced or reduced GO formed by the method provided herein has a capacitance of greater than or equal to between 1 mF/cm.sup.2 and 10 mF/cm.sup.2, 10 mF/cm.sup.2 and 100 mF/cm.sup.2, 100 mF/cm.sup.2 and 500 mF/cm.sup.2, and 500 mF/cm.sup.2 and 1000 mF/cm.sup.2. In some embodiments, a double-layer device comprising at least one electrode comprising the unreduced or reduced GO formed by the method provided herein has a conductivity of greater than or equal to about 0.1 siemens per meter (S/m), 0.5 S/m, 1 S/m, 10 S/m, 15 S/m, 25 S/m, 50 S/m, 100 S/m, 200 S/m, 300 S/m, 400 S/m, 500 S/m, 600 S/m, 700 S/m, 800 S/m, 900 S/m, 1,000 S/m, 1,100 S/m, 1,200 S/m, 1,300 S/m, 1,400 S/m, 1,500 S/m, 1,600 S/m, or 1,700 S/m. As such, the GO may therefore be used in a device such as, for example, a double-layer device, both before and after (e.g., see FIG. 7A) reduction. The performance of the two materials in, for example, a double-layer device may be substantially the same.

[0180] In some embodiments, the conductivity, the surface area, or the C:O ratio, of the CBO or rCBO is measured by methylene blue absorption.

Devices Comprising Carbon-Based Oxides and Reduced Carbon-Based Oxides

[0181] In some embodiments, the methods described herein synthesize CBO and rCBO materials capable of forming high performance double-layer capacitors, the areal capacitance of which is at least about 228 mF/cm.sup.2, wherein current methods may only be capable of forming double-layer capacitors, the areal capacitance of which is about 4.04 mF/cm.sup.2. As such, the methods described herein are capable of synthesizing CBO and rCBO materials which are capable of forming double-layer capacitors with a greater capacitance (e.g., at least about 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 times greater) than that formed by the CBO or rCBO materials formed by current methods.

[0182] The performance characteristics of an exemplary double-layer device (double-layer capacitor) was constructed from the CBO formed by the method provided herein (RR 3 at 45 min) are shown in FIG. 6 and TABLE 1.

TABLE-US-00001 TABLE 1 Scan Rate (mV/s) Capacitance (mF) Specific Capacitance (F/g) 10 229 265 20 192 223 40 159 185 60 140 164 100 118 137

[0183] FIG. 7A shows an exemplary cyclic voltammetry (CV) scan at a scan rate of 1,000 mV/s of a double-layer capacitor with electrodes comprising light-scribed rGO (ICCN) produced by the methods provided herein. FIG. 7B shows an exemplary cyclic voltammetry (CV) scan at a scan rate of 1,000 mV/s of a double-layer capacitor with electrodes comprising light-scribed GO materials, and non-light-scribed GO materials. As a CV scan of the exemplary device comprising electrodes formed of an unreduced GO synthesized by the methods disclosed herein (not shown) is essentially equivalent to the CV scan of the light-scribed rGO (ICCN) produced by the methods provided, per FIG. 7A, the effects of light-scribing may be insubstantial. In contrast, light-scribing alters the performance characteristics of the exemplary GO materials, per FIG. 7B. In some embodiments, the light-scribed rGO (ICCN) produced by the methods provided herein exhibit a capacitance at 1000 mV/s that is at least about 35 times greater than a capacitance of the light-scribed GO materials, and non-light-scribed GO materials.

[0184] FIG. 12 is a particle distribution chart of an exemplary CBO, per embodiments described herein. FIG. 13 is an X-Ray Diffraction (XRD) graph of an exemplary CBO, per embodiments described herein. FIG. 14 is an X-ray Photoelectron Spectroscopy (XPS) graph of an exemplary CBO, per embodiments described herein. FIG. 15 is a particle size distribution chart of an exemplary rCBO, per embodiments described herein. FIG. 16 is a Raman spectra of an exemplary rCBO, per embodiments described herein.

[0185] In some embodiments, exemplary sheets of GO material, per FIG. 17, are formed by drop-casting the GO material onto a silicon wafer, drying the GO material and the wafer for a period of time of about 12 hours, and coating the dried GO material with a thin layer of silicon dioxide (SiO.sub.2). The exemplary optical microscope images in FIG. 17 of the device formed thereby display the lateral size distribution of the GO sheets. Low and high magnification scanning electron microscope (SEM) image of an exemplary GO material on a silicon wafer, coated with SiO.sub.2 are show in FIGS. 18A and 18B, respectively.

Applications for Carbon-Based Oxide or Reduced Carbon-Based Oxide Materials

[0186] The CBO and rCBO materials described in the present disclosure may be used in a variety of applications including but not limited to: supercapacitors, batteries, energy storage device, catalysts, structural materials, water filtration, batteries, drug delivery, hydrogen storage, conductive inks, electronics, cars, aerospace technologies, inkjet printing, screen printing, printed circuit boards, radio frequency identification chips, smart fabrics, conductive coatings, gravure printing, flexographic printing, anti-static coatings, electrodes, electromagnetic interference shielding, printed transistors, memory, sensors, large area heaters, thermoelectric materials, lubricant, and thermal management systems.

[0187] In some embodiments, CBO and rCBO materials form reinforcements for polymers and oxides. In some embodiments, fibers formed from CBO and rCBO materials exhibit strong electrical and mechanical properties and serve as an alternative for carbon fibers currently used in car and aerospace industries. CBO and rCBO materials may be used in the fabrication of highly selective membranes that enable high flux rates and reduced energy consumption in filtering processes. CBO and rCBO electrodes may provide energy storage devices with high energy capacities. In some embodiments, CBO and rCBO materials exhibit may form supercapacitors with very high surface areas and capacitances. The water solubility and biocompatibility of some CBO and rCBO materials may form drug carrying devices. Finally, CBO and rCBO materials may be capable of efficiently storing hydrogen effectively.

Terms and Definitions

[0188] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Any reference to “or” herein is intended to encompass “and/or” unless otherwise stated.

[0189] As used herein, and unless otherwise defined, the term “about” refers to a range of values within plus and/or minus 10% of the specified value.

[0190] As used herein, and unless otherwise defined, the term “graphite oxide” and “graphene oxide” are used interchangeably. In some instances, graphite oxide and graphene oxide are collectively referred to herein as “GO.” For the purpose of this disclosure, the terms “reduced graphite oxide” and “reduced graphene oxide” are used interchangeably. In some instances, reduced graphite oxide and reduced graphene oxide are collectively referred to herein as “rGO.”

[0191] As used herein, and unless otherwise defined, the term “CBO” and “rCBO” refer to a carbon-based oxide and a reduced carbon-based oxide, respectively.

[0192] While preferred embodiments of the present disclosure have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the disclosure. It should be understood that various alternatives to the embodiments of the disclosure described herein may be employed in practicing the disclosure. It is intended that the following claims define the scope of the disclosure and that methods and structures within the scope of these claims and their equivalents be covered thereby.