Method of making hetero-atom doped activated carbon

Abstract

A method of making heteroatom-doped activated carbon is described in this application. Specifically, it describes a process that utilizes liquid furfuryl-functional-group compounds as starting materials, which are then used to dissolve the heteroatom containing source compounds, before being polymerized into solids using catalysts. The polymerized solids are then carbonized and activated to make the heteroatom-doped activated carbon. Electric double-layer capacitors (EDLC) were fabricated with activated carbons doped with boron and nitrogen, and tested for performance. Also, the boron and nitrogen content in the activated carbons was confirmed by chemical analysis.

Claims

1. A method of producing a heteroatom-doped activated carbon, comprising: a) mixing a liquid furfuryl-functional-group containing compound with the heteroatom containing source compound and a polymerization catalyst to form a mixture, wherein the heteroatom source compound is at least one of a tri-ethyl borate, nitric acid, NH.sub.3OH, boric acid, boron acetate, hexamethylenediamine and acrylonitrile, b) heating the mixture to polymerize the liquid furfuryl-functional-group compound and forming a polymerized solid; c) carbonizing the polymerized solid by heating under a controlled atmosphere, wherein the controlled atmosphere is an inert atmosphere, to form a carbonized solid; and d) activating the carbonized solid by heating under a controlled environment to form the heteroatom-doped activated carbon.

2. The method according to claim 1, wherein the liquid furfuryl-functional-group containing compound is at least one of a furfuryl alcohol, furfural, acetylfuran and 5-hydroxymethylfurfural.

3. The method according to claim 1, wherein the polymerization catalyst is at least one of an oxalic acid, maleic acid, benzoic acid, tartaric acid, formic acid, citric acid and acetic acid.

4. The method according to claim 1, wherein the controlled environment is one of a CO.sub.2, nitrogen, argon, or steam.

5. The method according to claim 1, wherein the heteroatom source compound is a tri-ethyl borate and the liquid furfuryl-functional-group containing compound is a furfuryl alcohol, wherein polymerization catalyst is at least one of an oxalic acid, maleic acid and tartaric acid.

6. The method of claim 1, further comprising adding an additive to the mixture of the heteroatom source compound, the liquid furfuryl-functional-group compounds and the catalyst, wherein the additive is at least one of a carbon black, graphene, carbon nanotubes and lignin.

7. The method of claim 1, wherein the polymerization step is carried out by heating at a temperature between 25 C. and 200 C.

8. The method of claim 1, wherein the carbonization is performed at a temperature between 600 C. and 800 C.

9. The method of claim 1, wherein the heteroatom containing source is boric acid dissolved in ethanol.

10. The method of claim 1, wherein the heteroatom-doped activated carbon is used for making electrodes for energy storage devices.

11. A method of producing a heteroatom-doped activated carbon, comprising: a) mixing a liquid furfuryl-functional-group containing compound with a heteroatom containing source compound to form a mixture, wherein the heteroatom containing source compound is also the polymerization catalyst, wherein the heteroatom containing source compound is boric acid in ethanol; b) heating the mixture to polymerize the liquid furfuryl-functional-group compounds and forming a polymerized solid wherein the liquid-furfuryl-functional group compound is at least one of a furfuryl alcohol, furfural, acetylfuran and 5-hydroxymethylfurfural c) carbonizing the polymerized solid by heating under a controlled atmosphere, wherein the controlled atmosphere is an inert atmosphere, to form a carbonized solid; and d) activating the carbonized solid by heating under a controlled environment to form the heteroatom-doped activated carbon.

12. A method of producing a heteroatom-doped activated carbon, comprising: a) mixing a liquid furfuryl-functional-group containing compound with more than one of a heteroatom containing source compound and a polymerization catalyst to form a mixture, wherein the heteroatom-containing source compounds are combinations of at least one of a urea and boric acid, a tri-ethyl borate and urea, an ammonium borate and urea, an tri-ethyl borate and hexamethylenediamine, a boron acetate and urea and a tri-ethyl borate and ammonium hydroxide; b) heating the mixture to polymerize the liquid furfuryl-functional-group containing compound and forming a polymerized solid; c) carbonizing the polymerized solid by heating under a controlled atmosphere, wherein the controlled atmosphere is an inert atmosphere, to form a carbonized solid; and d) activating the carbonized solid by heating under a controlled environment to form the heteroatom-doped activated carbon.

13. The method of claim 12, wherein the heteroatom-containing source compounds are tri-ethyl borate and urea, wherein the polymerization catalyst is at least one of an oxalic acid, tartaric acid, maleic acid, formic acid, benzoic acid and citric acid.

14. The method of claim 12, wherein the heteroatom-containing source compound are the ammonium borate in water solution and the urea in water solution, wherein the polymerization catalyst is at least one of an oxalic acid, tartaric acid, maleic acid, formic acid, benzoic acid and citric acid, and the furfuryl functional group compound is at least one of a furfuryl alcohol, furfural, acetylfuran, and 5-hydroxymethylfurfural.

15. The method of claim 12, wherein the heteroatom-containing source compounds are a solution of the boron acetate in water and the urea in water solution, wherein the polymerization catalyst is at least one of a boric acid, oxalic acid, tartaric acid, maleic acid, formic acid, benzoic acid and citric acid and the furfuryl functional group compound is at least one of a furfuryl alcohol, furfural, acetylfuran, and 5-hydroxymethylfurfural.

16. The method of claim 12, wherein the heteroatom-containing source compounds are an urea in water solution and a boric acid solution in an organic solvent, wherein the polymerization catalyst is at least one of an oxalic acid, tartaric acid, maleic acid, formic acid, benzoic acid and citric acid and wherein the liquid furfuryl-functional-group compound is at least one of a furfuryl alcohol, furfural, acetylfuran, and 5-hydroxymethylfurfural.

17. A method of producing a nitrogen-doped activated carbon, consisting of: a) dissolving a powdered urea in a liquid furfuryl-functional-group containing compound and adding thereto a polymerization catalyst to form a mixture, wherein the polymerization catalyst is at least one of a maleic acid, benzoic acid, tartaric acid, formic acid, citric acid, pyridine carboxylic acid and acetic acid; wherein the liquid furfuryl-functional-group containing compound contains furfuryl alcohol; b) heating the mixture to polymerize the liquid furfuryl-functional-group compound and forming a polymerized solid; c) carbonizing the polymerized solid by heating under a controlled atmosphere, wherein the controlled atmosphere is an inert atmosphere, to form a carbonized solid; and d) activating the carbonized solid by heating under a controlled environment to form the heteroatom-doped activated carbon.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1A and 1B: Flow chart of a process to make N- and B-doped activated carbon.

(2) FIG. 2: A representative set of charge/discharge curves from coin cells with B-doped carbons obtained from example 3.

(3) FIG. 3: A representative set of charge/discharge curves from coin cells with N-doped carbon and un-doped carbons, obtained from example 6.

DETAILED DESCRIPTION

(4) Recently, we have described a method to make activated carbon from furfuryl-functional-group containing liquid starting materials. The basic process involves: a. Starting with furfuryl-functional-group compounds like furfuryl alcohol, furfural and acetylfuran (amongst others) as a carbon source, and b. Mixing catalysts (silane as in U.S. Pat. No. 9,458,021, alumina powder as in U.S. patent application Ser. No. 15/208,336 or organic acids as in U.S. patent application Ser. No. 15/242,113) along with additives like carbon black into this carbon source, and polymerizing into a solid polymer; c. Carbonizing the solid polymer and activating the carbonized solid (using physical activation like CO.sub.2, and/or chemical activation described in U.S. patent application Ser. No. 15/255,128).

(5) We have also shown (e.g. U.S. patent application Ser. Nos. 15/242,113 and 15/255,128) that the activated carbons synthesized by these methods are suitable for EDLC applications, having measured capacitance values of 126 F/gm in organic electrolytes (1 molar tetra ethyl ammoniumtetra fluoroborate in acetonitrile), along with surface areas in excess of 2900 m.sup.2/gm and pore volumes in excess of 1.5 ml/gm. This method is now augmented to incorporate heteroatoms into the activated carbon, by adding heteroatom-containing compounds into the furfuryl-functional-group containing starting materials before polymerizingfollowed by subsequent processing steps described above.

(6) Boron-doped Activated Carbon

(7) FIG. 1a and FIG. 1b describe the process and variations of the process to make this boron-doped activated carbon along with N-doped activated carbon. In one of the embodiments, the current method starts with the dissolution of the heteroatom sources (101) into the starting materials (106). We have mainly used furfuryl alcohol (C.sub.5H.sub.6O.sub.2) as our starting material (carbon source), but have also evaluated furfural (C.sub.5H.sub.4O.sub.2) and acetylfuran (C.sub.6H.sub.6O.sub.2) with respect to their ability to dissolve the heteroatom source compounds. Other similar starting materials include 5-hydroxymethylfurfural (C.sub.6H.sub.6O.sub.3). The heteroatom sources need to be soluble in these starting materials, either directly or in a solution of organic solvents. For B-sources, we have used boric acid (H.sub.3BO.sub.3) which has negligible solubility in furfuryl alcohol and furfural, is insoluble in acetylfuran, but is soluble in methanol and ethanol (other alcohols are viable options too). We have evaluated the solubility of boric acid in ethanol. We found 3 gm of boric acid to be completely soluble in 50 ml of ethanol at room temperature (solubility of boric acid is generally accepted to be 12 wt. % in ethanol and 22 wt % in methanol at room temperature).

(8) Next, we evaluated the miscibility of the boric acid solution with the furfuryl-functional-group containing starting liquids. The boric acid solution was completely miscible in furfuryl alcohol, furfural and acetylfuran. Once the boric acid solution has been added to the carbon source, polymerization catalysts (102) were added to the carbon source. We have used oxalic acid, tartaric acid, maleic acid, benzoic acid and citric acid (individually or in combination), as the polymerization catalysts. Other organic acids like formic acid, lactic acid, acetic acid are also suitable as polymerization catalysts. After the addition of the polymerization catalysts, additives like carbon black (104) were added and the mixture and stirred thoroughly before being allowed to stand at room temperature to start the polymerization process (107). This was followed by heat treatments from 25 C. to 200 C. (108) to create a dense polymerized solid. With boric acid in solution in the carbon source, we have not found any significant change in the polymerization kinetics of the system. Polymerization conditions have been described earlier (U.S. patent application Ser. No. 15/242,113), and are followed here to create a dense polymerized solid. The polymerized solid is then carbonized and activated to make the heteroatom-doped activated carbon (109, 110, 111, 112).

(9) In one embodiment, 10 gm of boric acid was dissolved into 120 cc of ethanol and added to 141 cc of furfuryl alcohol to form a clear solution. To this, 5 gm of oxalic acid and 2.25 gm of carbon black were added. The mixture was polymerized at temperatures from 25 C. to 200 C., to make a dense polymerized solid.

(10) We have also used a combination of furfuryl alcohol (106) and furfural (106) as the carbon sourcewith a boric acid solution (101) as the heteroatom source. The catalysts (102) in this case were a combination of organic acids (oxalic, tartaric and maleic) and the additive was carbon black. A dense polymerized solid was obtained after heat treatment from 25 C. to 200 C. Additionally, we have also evaluated tri-ethyl borate as a source for B, and since this is a liquid, it was mixed directly with furfuryl alcohol. The procedure is similar to that described above. After the mixing of tri-ethyl borate and furfuryl alcohol, the polymerization catalyst was added, and allowed to form a dense polymerized solid. Other sources for B may also be used and include other tri-alkyl borates, ammonium borate, boron acetate and BF.sub.3 in MeOH. Any B-source that is not directly soluble in the liquid furfuryl-containing compounds as starting materials, is first dissolved in other organic solvents like methanol, ethanol or acetone, before addition to the carbon source.

(11) The use of the boric acid solution as a combination B-source and polymerization catalyst was also evaluated. In one embodiment, 12 gm of boric acid was dissolved into 130 cc of ethanol and added to a combination of 45 cc of furfuryl alcohol and 20 cc of furfural. This solution was then held at room temperature (with a cover to minimize evaporation) to allow polymerization to occur. After several hours, the clear liquid had turned black indicating the start of a polymerization reaction and further holding at room temperature resulted in thickening of the liquid and eventually a very viscous material. This was polymerized by soaking at 60 C., 100 C., and 200 C., to produce a dense polymerized solid. The apparent density of this material was measured to be 1.44 gm/ml using a liquid displacement method.

(12) Once a dense polymerized solid has been formed from any of the embodiments described above, the material is carbonized (109). This process is typically performed by heating under an inert atmosphere at temperatures between 600 C. and 800 C. The next step is an optional chemical activation step (110) that we recently described in U.S. patent application Ser. No. 15/255,128. We have found that the chemical activation step results in ultra-micropore sizes of <1 nm. Consequently, when these types of pores are desired in the final activated carbon, this chemical activation step is required. In one embodiment, the carbonized material was immersed in a dilute solution of 1.5M NaNO.sub.3 in a combination of water and ethanol (equal parts). The carbonized material was then removed from this solution and directly heated to 600 C. for 1 hour under nitrogen, to form the ultra-micropores.

(13) For a final physical activation step, the carbon is heated to temperatures between 900 C. and 1200 C. under a CO.sub.2 atmosphere (111), although most of our examples utilized 950 C. or 1000 C. as the activation temperature. Steam activation can also be used and is typically performed at lower temperatures than CO.sub.2 activation (800 C. to 1100 C.). After the activation step an activated carbon powder as heteroatom-doped activated carbon is obtained (112).

(14) To evaluate the performance of these B-doped carbons, EDLC devices were fabricated in the 2032 coin-cell format and tested for capacitance. B concentration in the carbon material was measured using the ICP-MS (Inductively Coupled Plasma Mass Spectroscopy) technique. Finally, surface area of the activated carbons was also measured using the BET (Brunauer, Emmett, and Teller) method (Brunauer, S., et al. 1938), along with measurements of pore volumes.

(15) Nitrogen-Doped Carbon

(16) For N-doped carbon, we have used urea as an N-source and found moderate solubility (8.5 wt. %) in furfuryl alcohol at room temperature. In one embodiment, 3 gm of urea powder (103) was dissolved into 30 ml of furfuryl alcohol at room temperature (106). Following this, 7 gm of maleic acid (102) was added and stirred (107) into solution at room temperature. After holding at room temperature for few hours, the solution started darkening in color signifying the onset of the polymerization reaction (108). At this stage, 0.45 gm of carbon black (104) was added and the mixture allowed standing at room temperature until it thickened and a pasty solid was obtained. This was then treated at 48 C., 100 C., and 200 C. to obtain a polymerized solid. In another embodiment, cross-linking agents like furfural are added to the furfuryl-alcohol/urea/polymerizing-catalyst solution described in the previous embodiment.

(17) In another embodiment, a solution containing urea is used as the N-source (103). Urea was found to be negligibly soluble in organic solvents like ethanol (only 5 gm urea in 100 ml). Urea is however highly soluble in waterwith about 108 gm of urea dissolving in 100 ml of water at 20 C. (Stumpe, et. al., 2007). To prepare a urea/water solution for use in our system, 25 gm of urea were dissolved in 35 ml of water by stirring at room temperature, resulting in a solution of 53 ml (with a density of 1.13 gm/ml). This urea solution (with a molar concentration of 11.9) was stirred until a clear solution was obtained and was then used as the nitrogen source. This 11.9M urea solution is completely miscible in furfuryl alcohol, but not miscible into furfural.

(18) In one embodiment, 30 ml of furfuryl alcohol was mixed with 4.32 gm of maleic acid and 1.68 gm of tartaric acid. 15 ml of a urea/water solution (11.9M) was then added, followed by 0.75 gm of carbon black. The mixture was allowed to stand at room temperature followed by polymerization heat treatments (25 C. to 200 C.) to make a dense polymerized solid.

(19) In another embodiment, the organic acids used to catalyze the polymerization reaction of furfuryl alcohol, are added to the urea/water solution first. This solution is then added to the furfuryl alcohol and allowed to polymerize. In this embodiment, a urea solution was first made by adding 10 gm of urea to 30 cc of water. Next 15 gm of tartaric acid was stirred into solution, and 20 cc of this solution was added to 30 cc of furfuryl alcohol to form a clear solution. Thereafter, 4 gm of maleic acid powder was dissolved into the liquid, followed by the addition of 0.5 gm of carbon black. The mixture was allowed to stand at room temperature and thickened into a pasty mass that held its shape when tilted. It was then heated at 48 C., 80 C., and 200 C. to form a hard polymerized solid suitable for carbonization and activation.

(20) In yet another embodiment, a urea/water solution was prepared by dissolving 10 gm of urea into 30 cc of water at room temperature. Once a clear solution was obtained, 10 gm of citric acid was added and stirred into the solution. Next, 20 cc of this solution was added to 30 cc of furfuryl alcohol, followed by 4 gm of maleic acid and 0.5 gm of carbon black. This mixture was then directly heated to 48 C., 120 C., and 200 C. to make a dense polymerized solid.

(21) Of the various organic acids used in our system, benzoic acid was found to be insoluble in the urea/water solution, while the addition of oxalic acid to the urea/water solution resulted in a white precipitate. Tartaric acid, maleic acid, and citric acid were found to be soluble in the urea/water mixture. Other organic acids can also be used, after first evaluating their solubility in the urea/water solution and suitability as a catalyst for the polymerization of furfuryl alcohol.

(22) In another embodiment, dimethyldichlorosilane (C.sub.2H.sub.6Cl.sub.2Si) was used as the polymerization catalyst for a furfuryl-alcohol urea solution (i.e. urea directly in solution in furfuryl alcohol). This solution was polymerized, followed by carbonization and activation. If no etching step is used to remove the residual Si that is left after the carbonization step, the final carbon will contain both Si and N as dopants. Chemical analysis using PIXE (proton-induced X-ray emission) methods on similar furfuryl-functional-group containing starting materials with dichlorodimethylsilane as a catalyst (described in U.S. Pat. No. 9,458,021) showed the presence of Si in the final carbon, but did not reveal any residual chlorine (from the silane). This embodiment cannot be used with a urea/water solution, since the presence of water will result in the hydrolysis of the silane.

(23) Hexamethylenetetramine (C.sub.6H.sub.12N.sub.4) was also evaluated as a potential N-source. The solubility limit of C.sub.6H.sub.12N.sub.4 in furfuryl alcohol was found to be 26 gm in 100 cc, at room temperature. 4 gm of C.sub.6H.sub.12N.sub.4 was dissolved in 35 cc of furfuryl alcohol, followed by 8 gm of maleic acid. Next, 0.8 gm of carbon black was added and the mixture allowed to stand at room temperature for polymerization to occur. Further heating at temperatures from 25 C. to 200 C., resulted in a dense polymerized solid.

(24) Other N-sources that can be used in the furfuryl-alcohol system include NH.sub.3OH, nitric acid (HNO.sub.3), acrylonitrile (CH.sub.2CHCN), hexamethylenediamine (C.sub.6H.sub.16N.sub.2) and some pyridines, amines, and azides. All of these N-sources need to either be liquid or soluble in solvents compatible with the liquid carbon source.

(25) The carbon source materials used to make our N-doped carbons include furfuryl alcohol, furfural, 2-acetylfuran, and 5-hydroxymethylfurfural. Both acetylfuran and hydroxymethylfurfural melt at 30 C., so working with these starting materials involves using temperatures slightly above room temperature in colder climates. Furthermore, urea is insoluble in furfural and acetylfuran. An 11.9M solution of urea in water was found to be immiscible in acetylfuran and furfural at room temperature. When heated to 120 C., furfural and the urea solution were still not miscible. When using furfural as the starting material, furfuryl alcohol may be added to the furfural/urea/water solution at room temperature, to dissolve the urea/water solution.

(26) In another embodiment, 10 cc of furfural was added to 20 cc of furfuryl alcohol and 20 cc of a urea/water solution (11.9M) to form a clear solution. 3 gm of maleic acid was then dissolved in the solution followed by 0.45 gm of carbon black. The mixture was allowed to stand at room temperature till it formed a pasty solid and was then heated at 48 C., 80 C., 120 C., and 200 C. to form a dense polymerized solid. In another embodiment, 15 cc of a 1:1 immiscible mixture of furfural and 11.9M urea solution in water, was added to 30 cc of furfuryl alcohol. Next, 4 gm of maleic acid was added, followed by 0.75 gm of carbon black. The mixture was then allowed to stand at room temperature till a pasty solid was formed. Polymerization was completed by heating from 25 C. to 200 C.

(27) Acetylfuran was also used as a carbon source for the method described in this application. The organic acids are selectively soluble in acetylfuran (e.g. oxalic acid will dissolve into acetylfuran, but benzoic acid does not). In one embodiment, 20 cc of acetylfuran was mixed with 12 cc of an 11.9M urea solution (in water). On mixing, a whitish residue was created. Next, 20 cc of furfural was added to the mixture and resulted in a clear solution. Next, 2 gm of oxalic acid was added to the solution and dissolved by stirring at room temperature. This was followed by 0.4 gm of carbon black and 10 cc of a maleic acid/urea/water solution (prepared by mixing 30 cc of water with 10 gm of urea and 5 gm of maleic acid). The mixture was allowed to stand at room temperature and started polymerizing into a pasty solid. It was then heated at 48 C., 100 C., and 200 C. to make a dense polymerized solid.

(28) Other nitrogen sources like hexamethylenetetramine were also evaluated with furfural and acetylfuran, but it was found to be insoluble in both. Others skilled in the art may recognize similar nitrogen source compounds that may be soluble and hence usable as N-sources in our system.

(29) Once a dense polymerized solid has been formed from any of the embodiments described above, the material is then carbonized. This process is similar to that described for the B-doped carbons. Additionally, the optional chemical activation step, also described for the B-doped carbons, can be used for the N-doped carbons as well.

(30) For a final physical activation step, the carbon is heated to temperatures between 900 C. and 1200 C. under a CO.sub.2 atmosphere. Steam activation can also be used and is typically performed at lower temperatures than CO.sub.2 activation (between 800 C. and 1100 C.). Nitrogen concentration in the carbons is measured using the CHN-method (ASTM D5291). As with the B-doped carbons, the surface area of the N-doped activated carbons was measured using the BET method.

(31) Finally, the process described here can also be used to make N and B co-doped carbons. For this embodiment, the process involves adding a boron source like boric acid in ethanol (101), to the furfuryl-containing starting materials (106), followed by the organic acid catalysts (102). After the mixture is stirred for at least 30 mins, the nitrogen source (103) is added (105) and the mixture is stirred (107) and polymerized (108). The rate of the polymerization reaction will depend on the amount of organic acids, urea, and boric acid, compared to the amount of furfuryl alcohol. Other combinations may also be used, including increased boric acid and urea concentrations or different B and N sources.

EXAMPLE 1

(32) In this particular embodiment of the method, we added 100 cc of tri-ethyl borate (T59307, Sigma Aldrich, St. Louis, Mo.) to a combination of 125 cc of furfuryl alcohol and 150 cc of acetone (HPLC grade). The mixture was then thoroughly stirred at room temperature for 30 minutes, and 30 ml of dichlorodimethylsilane (440272, Sigma Aldrich, St. Louis, Mo.) was added slowly over a period of 30 minutes while stirring. The mixture was then covered with a lid to minimize evaporation losses and allowed to stand at room temperature for several hours. The mixture started polymerizing at room temperature and was held there until the rate of weight loss approached zero. Next, to complete the polymerization, the material was directly subjected to a 200 C. treatment, under air, until the rate of weight loss was negligible. Next, the polymerized material was subjected to a carbonization treatment. The material was loaded onto a quartz boat (10 cm long by 4 cm wide) that was inserted into a tube furnace (model GSL-1100X, MTI Corporation, Richmond, Calif.). Carbonization was done at 600 C., under nitrogen. Next, the carbonized material was activated. This was also done in a quartz tube furnace, with the carbon being heated up to the activation temperature of 1000 C. under nitrogen. CO.sub.2 flowing at 3.4 liters/minute, was used to activate the carbon, until 23% weight loss was obtained (77% yield).

(33) To evaluate the amount of boron in the final activated carbon, we have used Inductively Coupled Plasma Mass Spectrometry (ICP-MS) techniques to measure the B-content. With this technique, acid digestion of the sample is used to make a solution that is atomized with argon gas into hot plasma. The sample is then excited, emitting light wavelengths characteristic of its elements. The technique has a detection limit of <1 ppm. Using ICP-MS, we measured 2.97 wt. % of B in the as-activated sample (Table 2), indicating that tri-ethyl borate is a suitable B-source, for making B-doped carbons from the furfuryl-functional group containing liquid starting materials. This particular example also includes Si as a dopant in the carbon (from the dichlorodimethylsilane catalyst).

(34) TABLE-US-00002 TABLE 2 Properties of B-doped activated carbon prepared by methods described in example 1. CO.sub.2 Carbon Heteroatom activation Boron Example source source Catalyst yield content 1 Furfuryl Tri-ethyl Dichloro- 77% (23% 2.97 alcohol borate dimethylsilane burn-off) wt. %

EXAMPLE 2

(35) In this embodiment of the method, 150 cc of Furfuryl alcohol (W249106, >=98%, Sigma-Aldrich, St. Louis, Mo.) was stirred for few minutes in a glass jar using an overhead stirrer operating at around 200 rpm. Next, 10 gm of boric acid H.sub.3BO.sub.3 (B6768 Sigma Aldrich, St. Louis, Mo.) powder was added to the furfuryl alcohol and the mixture, along with 35 cc of reagent alcohol (241000200, Pharmco-Aaper, Shelbyville, Ky.). The alcohol composition was 90.65% ethanol, 4.53% methanol and 4.82% isopropyl alcohol. The mixture was stirred until all the boric acid was in solution. Next, 2.25 gm of carbon black (C-NERGY SUPER C45) was added, along with 2 gm of citric acid (251275, Sigma Aldrich, St. Louis, Mo.), and the mixture stirred for an additional 160 minutes. It was then allowed to stand at room temperature, under air, until no further significant weight loss was observed and a pasty solid material was obtained. Following this, the material was subjected to heat treatments at 48 C., 78 C., 120 C., and 200 C., all under air, to create a dense polymerized solid.

(36) Next, the polymerized solid was carbonized at 600 C. for 1 hour under nitrogen in a quartz tube furnace. The carbonized material was then subjected to a chemical activation method described in an earlier filing (U.S. application Ser. No. 15/255,128). This process involved immersing the carbonized material into a solution of NaNO.sub.3 in water and alcohol, followed by heat treatments and washing. Accordingly, a solution of 25 gm of NaNO.sub.3 (Lab-Pro ZS0655, Sunnyvale, Calif.) in 100 cc of de-ionized water (resistivity of 18.01 megohm-cm) and 100 cc of reagent alcohol (241000200, Pharmco-Aaper) was made at room temperature. The carbonized material was immersed in this solution for several hours under air. During this time, the mixture was ultrasonically vibrated for 60 minutes. Next, the carbonized material was removed, rinsed and heated to 200 C. under air for several hours, followed by boiling and rinsing steps (in DI-water) to remove residue from the NaNO.sub.3 treatment. Next, the material was activated in a quartz tube furnace at 950 C. with CO.sub.2 flowing through the tube at 3.4 liters/min. Heating was continued until 21% of the original weight of the carbon remained (i.e. burn-off 79%, by weight).

(37) Measurement of the surface area of this activated carbon powder was done using the BET (Brunauer, Emmett, and Teller) method. Measurements were made on a Micromeretics TriStar II 3020 instrument, using nitrogen as the adsorptive gas. Nitrogen isotherms were obtained at 77K after the samples were degassed for 1 hour at 90 C., followed by 16 hours at 300 C. The isotherms were fitted to the BET equation to obtain surface area. The results are shown in Table 3. Boron content was measured by ICP-MS techniques and the results are also included in Table 3, indicating that Boric-acid/ethanol solution is also a suitable heteroatom source for B-doped carbons made from furfuryl-functional-group containing liquid starting materials.

(38) TABLE-US-00003 TABLE 3 Properties of B-doped activated carbon prepared by methods described in example 2. Hetero- CO.sub.2 BET Boron Exam- Carbon atom activation area content ple Source source Catalyst yield (m.sup.2/gm) (wt. %) 2 Furfuryl Boric acid/ Organic 21% 2624.52 0.45 alcohol ethanol acid

EXAMPLE 3

(39) This embodiment of the method utilizes similar ratios of boric acid to furfuryl alcohol but uses larger quantities of organic acid catalysts to polymerize the boric-acid/furfuryl-alcohol mixture. Specifically, 10 gm of boric acid (Sigma Aldrich) was dissolved in 100 ml of reagent alcohol (90.65% ethanol, 4.53% methanol, and 4.82% isopropyl alcohol), by stirring for 30 minutes at room temperature. Separately, 141 cc of Furfuryl alcohol (Sigma-Aldrich) was stirred for few minutes in a glass jar using an overhead stirrer operating at around 200 rpm. Next, the boric acid solution was added to the furfuryl alcohol and the solution was stirred for an additional 30 minutes. Then, 4.93 gm of oxalic acid (75688, anhydrous, 99.0%, Sigma-Aldrich, St. Louis, Mo.) and 2.25 gm of carbon black (C-NERGY SUPER C45) were added to this solution and stirring was continued for another 60 minutes. The mixture was then allowed to stand at room temperature for several hours until the rate of weight loss was negligible. This was followed by heat treatment at 80 C., under air, which was continued until the rate of weight loss became negligible. The solid was then heated at 120 C. and 200 C., under air, to create a polymerized solid.

(40) Next, the polymerized material was prepared for carbonization at 600 C. This was done in one step by soaking at 600 C. under nitrogen, in a quartz tube furnace. The carbonized material was then subjected to our chemical activation step. A solution of 25 gm of NaNO.sub.3 in 100 cc of de-ionized water and 100 ml of reagent alcohol, similar to that described in Example 2. The carbonized material was immersed in this solution and allowed to soak for several hours under air, with a cover to minimize evaporation losses of the liquid. It was then removed from the solution, rinsed in de-ionized water and heated in an oven at 200 C. for several hours, also under air. Next, the carbon was thoroughly washed by boiling in de-ionized water and rinsing several times to remove any remaining NaNO.sub.3 or related by-products. The carbon was then further activated using CO.sub.2. This was done at 950 C., in a quartz tube furnace with CO.sub.2 flowing through the tube at a rate of 3.4 liters/min. Activation yield of 25% was achieved (i.e. burn-off 75%) for the CO.sub.2 activation step.

(41) We have then used this boron-doped activated carbon to build EDLC devices and evaluated the electrical performance of these devices. The material was first ground down to an average size of 20 to 30 microns in preparation for EDLC electrode manufacturing. In this case, a dry electrode method was used (mixing TEFLON powderPTFE 6C from DuPont Corporation, Wilmington, Del.with the carbon; followed by rolling onto aluminum foil substrates). 2032 sized coin-cell electrodes were punched out and fabricated into coin cells using a standard 1M tetraethyl ammonium tetra fluoroborate/Acetonitrile organic electrolyte, commonly used in commercial EDLC manufacturing (B-doped carbon in both electrodes). Charge/discharge experiments were carried out and capacitance values were calculated from the slope of the discharge curves. FIG. 2 shows a representative set of charge/discharge curves for EDLC devices fabricated using the carbons from this embodiment. The average value of the specific capacitance measured from the discharge curves is shown in Table 4. This indicates that B-doped carbons made from Boric-acid/furfuryl-functional-group containing liquid starting materials, are also capable of high specific capacitance in EDLC applications.

(42) TABLE-US-00004 TABLE 4 Properties of a B-doped carbon prepared by techniques described in example 3. CO.sub.2 Specific Carbon Heteroatom activation capacitance Example source source Catalyst yield (F/g) 3 Furfuryl Boric acid/ Organic 25.1% 121.2 alcohol ethanol acid

EXAMPLE 4

(43) In this embodiment. 6 gm of Boric acid was dissolved in 105 ml of reagent alcohol (90.65% ethanol, 4.53% methanol, and 4.82% isopropyl alcohol), by stirring at room temperature. Separately, 45 ml of Furfuryl alcohol (Sigma-Aldrich) was stirred for few minutes in a glass jar using an overhead stirrer operating at around 200 rpm. Next, the boric acid solution was added to the furfuryl alcohol and the solution was stirred to thoroughly mix it. Next, 3 gm of Boric acid was mixed into 27.5 ml of the reagent alcohol and added to 20 ml of Furfural. This mixture was stirred using an overhead stirrer till all the Boric acid was in solution. Then, the furfural/Boric-acid solution was added to the furfuryl-alcohol/Boric-acid solution and an additional 3 gm of Boric acid in 50 ml of reagent alcohol was added to the mixture. This solution was then polymerized at 60 C., under airuntil the rate of weight-loss approached zero. A solid material was formed at this stage and it was further heated at 120 C. and 200 C. to complete the polymerization process. Next, the polymerized material was carbonized at 600 C. for 60 mins under nitrogen, followed by CO.sub.2 activation at 950 C., both in a quartz tube furnace. Activation was carried out till a weight loss of 54% was achieved. The B-content of the activated carbon was then measured using the ICP-MS method, and a value of 2.9 wt. % was reported (shown in Table 5). It can be seen from this example that the B-source used here (i.e. Boric acid) is also a suitable catalyst for the polymerization of the furfuryl-functional-group containing liquid starting materials (a combination of furfural and furfuryl alcohol in this case), with no additional catalysts being required here.

(44) TABLE-US-00005 TABLE 5 Properties of a B-doped carbon prepared by techniques described in example 4. CO.sub.2 Boron Carbon Heteroatom activation content Example source source Catalyst yield (wt. %) 4 Furfuryl Boric acid/ None 46% 2.90 alcohol + ethanol Furfural

EXAMPLE 5

(45) In this embodiment of the method, 50 cc of furfural (C.sub.5H.sub.4O.sub.2) (185914, Sigma Aldrich, St. Louis, Mo.) was stirred for a few minutes in a beaker with an overhead stirrer operating at 200 rpm under air. Next, a combination of organic acids was added to the furfural, starting with 1.27 gm of oxalic acid (75688, anhydrous, 99.0%, Sigma-Aldrich, St. Louis, Mo.), followed by 1.63 gm of maleic acid, (M0375, 99.0% (HPLC), from Sigma Aldrich St. Louis, Mo.) and 2.1 gm of tartaric acid (T109, 99.5%, from Sigma Aldrich St. Louis, Mo.). After all the acid powders were in solution, stirring was continued for another 90 minutes. The solution was then allowed to stand at room temperature for several hours, before 0.75 gm of carbon black (C-NERGY SUPER C45 from Imerys, Willebroek, Belgium) was added. Next, 36 gm of urea powder (U5378, Sigma Aldrich, St. Louis. Mo.) was added to 35 cc of de-ionized water to make a solution. This solution was then added directly to the furfural/organic acid mixture. This mixture of the two solutions was then thoroughly mixed using an overhead stirrer. The mixture was then allowed to soak at room temperature, until it became a pasty solid. This solid material was then heated at 78 C., 120 C., and 200 C., under air. Heating at each temperature was carried out until the rate of weight loss of the material approached zero, before the next treatment was started. Next, the solid polymerized material was carbonized in a quartz tube furnace by heating at 600 C. for 1 hour, under nitrogen. The carbonized material was then activated in the quartz tube furnace at 950 C. with CO.sub.2 flowing through the tube at 3.4 liters/min. Activation was continued until a yield of 21.3% was obtained (i.e. a 78.7% burn-off, by weight).

(46) This activated carbon with N-doping was then evaluated for N-content using CHN analysis techniques. The sample was combusted in oxygen, carried through the system by helium, converted and measured as CO.sub.2, H.sub.2O, and N.sub.2per the ASTM D5291. The product gases were separated and detected by thermal conductivity or IR with a detection limit of 0.10%. The results for N-content are shown in Table 6.

(47) Finally, we have also measured the surface area of this activated carbon powder using the BET method. Measurements were made on a Micromeretics TriStar II 3020 instrument, using nitrogen as the adsorptive gas. Nitrogen isotherms were obtained at 77K after the samples were degassed for 1 hour at 90 C., followed by 16 hours at 300 C. The isotherms were fitted to the BET equation to obtain surface area. The results are included in Table 6, indicating that urea is a suitable N-source for making N-doped carbons from furfuryl-functional-group containing liquid starting materials, and that these N-doped carbons can also be activated to high specific surface areassuitable for EDLC applications.

(48) TABLE-US-00006 TABLE 6 Properties of N-doped activated carbon prepared by methods described in example 5. Hetero- BET N Exam- Carbon atom Activation area content ple source source Catalyst yield (m.sup.2/gm) wt. % 5 Furfural Urea/ Organic 21.3% 2546 3.12 water acids

EXAMPLE 6

(49) In this embodiment, 150 cc of Furfuryl alcohol (W249106, >=98%, Sigma-Aldrich, St. Louis, Mo.) was stirred for few minutes in a glass jar using an overhead stirrer operating at around 200 rpm. Next, 14 gm of urea (U5378, Sigma Aldrich, St. Louis. Mo.) was added and stirred for 1 hour to dissolve it. Next, 20 gms of maleic acid was added and stirred for an additional 1 hour, before 2.25 gms of carbon black (C-NERGY SUPER C45 from Imerys, Willebroek, Belgium) was added. The mixture was then heated at 35 C., 48 C., 80 C., 120 C., and 200 C., under air to form a dense polymerized solid.

(50) The polymerized solid was then carbonized by heating it to 600 C. under nitrogen. Activation was carried out at 1000 C. under CO.sub.2 until 74% weight-loss was obtained. For this activated carbon, we measured the iodine number (per ASTM D4607) to be 1592 mg/gm (shown in Table 7). This is similar to the industry-standard activated carbon used for EDLC electrodes (namely, the YP-50 brand of carbon from Kuraray Chemical Co. in Japan).

(51) To evaluate the performance of our N-doped carbons, we have also tested it in EDLC configurations. Specifically, the carbon was ground to a d.sub.50 size of 5 m, and a slurry method using SBR/CMC (Styrene Butadiene Rubber/Carboxy Methyl Cellulose) was employed to make electrodes (on aluminum foil substrates). These electrodes were then cut to fit in 2032 sized coin cells. Also, similar electrode manufacturing methods were used to make electrodes with the industry-standard YP-50 brand of carbon. Two configurations of coin cells were then made (a) using YP-50 carbon for both electrodes and, (b) one YP-50 electrode and one N-doped carbon electrode (made from carbon obtained from the process described in this example). Charge/discharge curves were obtained over several 100's of cycles and the capacitance of the cells was calculated from the slope of these curves. FIG. 3 shows a representative set of charge/discharge curves for the second configuration described above. Discharge capacitance (measured from the slope of the discharge curve) was found to be 0.253 Farads/coin-cell. Similar measurements on the symmetric YR-50 coin cells resulted in a discharge capacitance of 0.25 Farads/coin-cell. This indicates the suitability of using urea as an N-source to make N-doped carbons (from furfuryl-functional-group containing liquid starting materials), suitable for EDLC applications. Also, this N-doped carbon is shown to be a suitable material for asymmetric EDLC devices using N-doped and un-doped carbons for the two electrodes.

(52) TABLE-US-00007 TABLE 7 Properties of N-doped activated carbon prepared by methods described in example 6. Capaci- Hetero- CO.sub.2 tance/ Exam- Carbon atom Activation Iodine coin-cell ple source source Catalyst yield (mg/gm) (F) 6 Furfuryl Urea Organic 26% 1592 0.253 alcohol acid

EXAMPLE 7

(53) In this embodiment, we have built an asymmetric coin-cell capacitor by using one B-doped electrode (as the cathode) and an N-doped electrode as the anode. The N-doped carbon is from Example 6, while the B-doped carbon is made as follows. 10 gm of Boric acid was first dissolved in 108 ml of reagent alcohol. This was added to 150 ml of furfuryl alcohol, followed by 6.3 gm of tartaric acid, 4.89 gm of maleic acid and 3 gm of oxalic acid. The mixture was stirred until all the acids were in solution. Next 2.25 gm of carbon black was added and stirred for an additional 2 hours. Following this, the mixture was allowed to stand at room temperature until it thickened and the rate of weight loss approached zero. Polymerization was completed by heating at 85 C., 120 C. and 200 C. Next, carbonization was done at 600 C. for 1 hour under nitrogen, followed by CO.sub.2 activation at 950 C. (activation yield of 32%).

(54) This B-doped carbon (similar to that obtained in examples 2 and 3) was used to make EDLC electrodes using the slurry method described earlier (example 6). 2032 coin cells were made with the B-doped carbon as the cathode and the N-doped carbon (from example 6) as the anode. Charge/discharge curves were measured and capacitance of the coin cells was measured to be in 0.25 Farad/coin-cell. Charge/discharge curves from this asymmetric EDLC are similar to those shown in FIG. 5. Details of this embodiment are shown in Table 8. This example indicates the feasibility of making asymmetric EDLC devices from a B-doped and an N-doped electrode.

(55) TABLE-US-00008 TABLE 8 Properties of N-doped and B-doped carbon used for asymmetric EDLC devices. CO.sub.2 Carbon Heteroatom Activation Capacitance/ Example #7 source source Catalyst yield coin-cell (F) N-doped Furfuryl Urea Organic 26% 0.25 alcohol acid B-doped Furfuryl Boric acid/ Organic 32% alcohol ethanol acid

(56) We have discussed a number of examples and embodiments of the invention and those skilled in the art will recognize that modifications, permutations, additions, and sub-combinations can be made to produce the same final result. It is therefore intended that any claims hereafter introduced based on the descriptions and drawings detailed above are interpreted to include all such modifications, permutations, additions, and sub-combinations to be within their spirit and scope. As used herein, the term embodiment means an embodiment that serves to illustrate by way of example but not limitation.

INDUSTRIAL APPLICABILITY

(57) Benefits of producing both B-doped and N-doped carbons is clear from the data in table 1. Relevant applications of these heteroatom-doped carbons include electrodes for capacitors like electric double layer capacitors (EDLCs), carbon-dioxide capture (in the case of N-doped carbons), and oxygen reduction in fuel cells (for B-doped carbons). Besides these, carbons doped with heteroatoms like sulfur have also been used for EDLC electrode applications, while silicon-doped carbons are attractive for hydrogen storage. For the EDLC applications, typical capacitance values for the carbons used today are 100 farads/gm with organic electrolytes, 200 farads/gm with aqueous electrolytes. While ionic electrolytes are under development, and aqueous electrolytes only support very low cell voltages, organic electrolytes are the most common industrial configuration of the large EDLC devices today. Also, the acceptable surface area values of carbons for these EDLC applications are between 1500 and 1600 m.sup.2/gm. It is clear from table 1, however, that none of the described methods for B-doped carbons have resulted in activated carbon with high surface area or high capacitance. Hence the need exists for a simple process that produces B-doped carbons with high surface areas and high capacitance values for use in EDLC devices. This is shown in examples 2 and 3 of the instant application.

(58) For N-doped carbons (shown in table 1) derived from synthetic starting materials, the measured surface areas are typically low. For the method that resulted in high surface area (synthetic starting materials), the EDLC performance was not measured, but more importantly, a hazardous air pollutant was used as one of the starting materials. Consequently, a simple process to make N-doped activated carbon is desired that results in a high surface area and does not use hazardous air pollutants as starting materials. This is shown in example 5 of the instant application.

(59) Furthermore, constructing an asymmetric EDLC with one B-doped activated carbon electrode combined with an un-doped carbon electrode, or one N-doped activated carbon electrode combined with an un-doped carbon electrode, or one B-doped activated carbon electrode combined with one N-doped activated carbon electrode, has the promise of improving performance over EDLC devices made from un-doped carbons. Asymmetric EDLC devices are described in examples 6 and 7 of the instant application.