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WO2018067292A1 - Procédé de fabrication de charbon actif dopé par hétéroatomes - Google Patents

Procédé de fabrication de charbon actif dopé par hétéroatomes Download PDF

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WO2018067292A1
WO2018067292A1 PCT/US2017/051944 US2017051944W WO2018067292A1 WO 2018067292 A1 WO2018067292 A1 WO 2018067292A1 US 2017051944 W US2017051944 W US 2017051944W WO 2018067292 A1 WO2018067292 A1 WO 2018067292A1
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heteroatom
acid
doped
carbon
solution
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Shantanu Mitra
Vinod Nair
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Farad Power Inc
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Farad Power Inc
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Priority claimed from US15/242,113 external-priority patent/US9938152B2/en
Priority claimed from US15/255,128 external-priority patent/US9975778B2/en
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Publication of WO2018067292A1 publication Critical patent/WO2018067292A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • This disclosure generally relates to a method of making heteroatom-doped activated carbon.
  • heteroatom-doped carbon [003] Several methods for making heteroatom-doped carbon have been found in literature. For example, boron (B)-doped carbons have been synthesized using a number of different methods and have recently been evaluated as electrode materials for electric double-layer capacitors (EDLCs) and 0 2 reduction applications in fuel cells. Similarly, nitrogen (N)-doped carbons have also been evaluated as EDLC electrode materials, along with other applications like C0 2 capture and storage.
  • B electric double-layer capacitors
  • N nitrogen-doped carbons
  • a mesoporous B-doped carbon was synthesized by co -impregnation of sucrose and boric acid into a mesoporous silica template (SBA-15), followed by carbonization and etching of the template (Wang, D.W., et. al., 2008).
  • SBA-15 mesoporous silica template
  • Maximum B-doping levels of 0.6 atomic % ware reported using this method, along with a specific surface area of 660 m /gm.
  • Specific capacitance of EDLC devices using this B-doped carbon was found to be -1.5 times higher than with boron-free carbon, using aqueous electrolytes.
  • US Patent 7919014 described a method to make B-doped activated carbon by mixing an activated carbon powder with a boric acid solution (maximum B % calculated for the mixture was 1.0 atomic %, although the actual atomic % of B in the final carbon was not reported). This mixture was then dried and heated to form the B-doped carbon. It is unclear whether B entered the carbon matrix with this technique or remained within surface functional groups.
  • B-doped graphene nano-sheets (with a maximum of 2.56 atomic % B) were synthesized for use as electrode materials; and capacitance values were compared against similarly synthesized materials that were not doped with B.
  • the capacitance values of the B-doped materials were 2 times higher than the noii-B -doped materials, in aqueous electrolytes.
  • the B-doped graphene nano-sheets were synthesized by first thermally reducing graphene oxide, followed by mixing this with boric acid in ethanol and autoclaving at 150°C (Thirumal, V., et. al., 2016).
  • N-doped activated carbons were prepared from chitosan (a biomass precursor obtained from shrimp shells, naturally containing N) (Sliwak, A., et. al., 2016). The process involved high temperature carbonizing, followed by C0 2 activation. These carbons were found to have a maximum of 5.4 wt.% N - with specific surface area and specific capacitance values of 1080 m /gm and 147 F/gm (in aqueous electrolytes), respectively.
  • N-doped carbons have also been made from synthetic starting materials.
  • a nitrogen-doped porous carbon nanofiber (CNF) structure was synthesized with 4 to 12.14 atomic % N, by mixing the CNF with pyrrole and ammonium persuifate, and carbonizing at temperatures of 1100°C (Chen, L.F., et. al., 2012). These carbons had specific surface areas of 562 mVgm and capacitance values that varied with the N-content (7.22 atomic % N showed the best capacitance).
  • N-doped carbon was synthesized using a soluble resol as a carbon source, dicyandiamide as a nitrogen source, and a surfactant (Pluronic®F127) as a soft template. Following carbonization and pyrolysis (to remove the template), the material was chemically activated using KOH, to obtain a surface area of 494-586 m7gm. A maximum N- content of 13.1 wt.% was achieved and performance of these carbons for C0 2 -capture applications (3.2 mmol/gm, at 298K, l.Obar) and EDLC applications (262 F/gm in aqueous electrolytes) was measured (Wei J, et. al., 2013).
  • N-doped carbon was synthesized from the well established urea- formaldehyde condensation reaction by adding furfuryl alcohol to the system prior to co- polymerizing the mixture (Liu, Z., et. al. 2015).
  • This method of co-polymerization involved the polymerization of a furfuryl alcohol and a urea/formaldehyde system - simultaneously.
  • There are several issues with this approach (i) the kinetics of the urea/formaldehyde condensation reaction are different from the kinetics of the furfuryl alcohol polymerization reaction; (ii) during the carbonizing stage, the volatile organic compounds that are typically released here, are also different.
  • N-doped carbon was made using a surfactant-controlled zeolitic imidazolate framework (ZIF-8) [Liu, N.L., et. al., 2016].
  • ZIF-8 zeolitic imidazolate framework
  • a solution of zinc nitrate was added to a solution of 2-methylimidazole and polyvinylpyrrolidone (PVP) at room temperature and aged for 10 hours.
  • PVP polyvinylpyrrolidone
  • Measurements of capacitance using aqueous electrolytes resulted in 200 F/gm.
  • a maximum N-doping of 15 wt. % was measured, along with a specific surface area of 798 m7gm.
  • Table 1 The various methods of doping carbon with nitrogen and boron described above are summarized in Table 1.
  • Nano fiber m 2 /gm atomic % (aqueous)
  • N 2.93 Liu, Z., aldehyde + Co-Polymer2273 Not
  • Zeolite N 15 Liu, imidazole; imidazole; ⁇ 800 ⁇ 200F/gm
  • the instant application discloses a method of producing heteroatom-doped activated carbon in simple steps.
  • a liquid furfuryl-functional-group compound (the carbon source) with a heteroatom containing compound (written in alternative lanuage throughout the specificaiton as the heteroatom source, heteroatom source containing compound or compounds) and a polymerization catalyst (catalyst) to make an activated heteroatom-doped carbon via a single stage polymerization reaction, a carbonization treatment and an activation treatment, is described.
  • the carbon source is a liquid that can dissolve the heteroatom source and the catalyst.
  • the heteroatom source is first dissolved in an organic solvent (e.g.
  • heteroatom containing compound is not soluble common organic solvents, then a water-based solution of the heteroatom compound is added to the liquid carbon source, followed by the catalyst and polymerization.
  • polymerization is carried out over a temperature range of 25°C - 200°C, in air.
  • the polymerized solid is carbonized by heating at temperatures between 600°C and 800°C under an inert atmosphere, and then activated - either chemically using our previously described process in US patent application 15255128, or with activation methods typically used in the industry (example C0 2 or steam activation at temperatures typically between 900°C and 1100°C).
  • the carbon is first heated to the activation temperature under an inert atmosphere of nitrogen or argon, and then the activating gas (C0 2 or steam) is used. Cooling is done under an inert atmosphere.
  • an additive is also added to the carbon-source/heteroatom- source/catalyst solution, before polymerization.
  • This additive is not soluble in the liquid carbon source, and is in the form of a fine powder.
  • the additive is thoroughly mixed into the liquid before polymerization begins.
  • the additive is a material that that enhances the performance of the activated carbon in the end application.
  • activated carbon that is used for EDLC electrodes is mixed with a high-conductivity carbon powder like carbon black or carbon nanotubes or graphene.
  • These types of materials form the additives used in the current method. Specifically, carbon black, carbon nanotubes, carbon nanofibers, graphenes, and similar materials can call be added as additives to the carbon source in our method.
  • the liquid carbon source comprises of a multitude of furfuryl- functional-group containing liquids. It has been shown earlier that furfural can act as a cross- linking agent in the curing step of a two-stage process using a combined furfural/furfuryl- alcohol system for making hard, chemically resistant resins for cements and coatings (US patent
  • the heteroatom source is dissolved in one of the liquid furfuryl-functional- group compounds, while the catalyst is added to the other liquid furfuryl-functional-group compound.
  • the heteroatom containing compound is not directly soluble in the carbon source, then it is first dissolved in an organic solvent or water.
  • the catalyst and the heteroatom source are the same.
  • This catalyst/heteroatom source is dissolved into the carbon source, followed by polymerization, carbonization and activation, to form the heteroatom-doped activated carbon.
  • the characteristics of the combined heteroatom/catalyst source are that the compound has both an acidic nature - with a pKa (acid dissociation constant) value between 1 and 10, and also contains the desired heteroatom to dope the final carbon.
  • this compound are boric acid (B- heteroatom, with a pKa of 9.24), 2,3 -pyridine dicarboxylic acid (N-heteroatom, with a pKa of 2.43); 2,4-pyridine dicarboxylic acid (N-heteroatom, with a pKa of 2.15); 3,5-pyridine dicarboxylic acid (N-heteroatom, with a pKa of 2.8).
  • the polymerization catalysts are first added to the liquid furfuryl-functional-group compound before the heteroatom containing compounds.
  • the heteroatom compounds may be added in the form of a solution. The remaining process steps are similar to those described above.
  • the polymerization catalysts are first dissolved into a solution containing the heteroatom compounds to make a catalyst/heteroatom compound solution.
  • catalyst/heteroatom compound solution is added directly to the carbon source and processed as outlined earlier.
  • heteroatom-doped carbons produced by these methods were measured for heteroatom doping levels and specific surface area. Also, in some cases, EDLC coin cells were fabricated using these carbons - for evaluation of charge/discharge curves and capacitance.
  • Figure 1 A and I B Flow chart of a process to make N- and B-doped activated carbon.
  • Figure 2 A representative set of charge/discharge curves from coin cells with B-doped carbons obtained from example 3.
  • Figure 3 A representative set of charge/discharge curves from coin cells with N -doped carbon and un-doped carbons, obtained from example 6.
  • Figure la and Figure lb describe the process and variations of the process to make this boron-doped activated carbon along with N-doped activated carbon.
  • the current method starts with the dissolution of the heteroatom sources (101) into the starting materials (106).
  • Other similar starting materials include 5- hydroxymethylfurfural (C ⁇ h)-
  • the heteroatom sources need to be soluble in these starting materials, either directly or in a solution of organic solvents.
  • boric acid H 3 BO 3
  • H 3 BO 3 boric acid
  • 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 (US patent application 15242113), 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).
  • lOgm 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 20()°C, to make a dense polymerized solid.
  • B may also be used and include other tri-alkyl borates, ammonium borate, boron acetate and BF 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.
  • boric acid solution as a combination B-source and polymerization catalyst was also evaluated.
  • 12 gm of boric acid was dissolved into 130 cc of ethanol and added to a combination of 45cc of furfuryl alcohol and 20cc 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, 10G°C, and 200°C, to produce a dense polymerized solid. The apparent density of this material was measured to be 1.44gm/ml using a liquid displacement method.
  • 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 (1 10) that we recently described in US Paten Application 15255128. We have found that the chemical activation step results in ultra-micropore sizes of ⁇ 1 nm.
  • the carbonized material was immersed in a dilute solution of 1.5M NaN0 3 in a combination of water and ethanol (equal parts). The carbonized material was then removed from this solution and directly heated to 60()°C for 1 hour under nitrogen, to form the ultra-micropore s.
  • the carbon is heated to temperatures between 900°C and 1200°C under a COo atmosphere (111), although most of our examples utilized 950°C or !000°C as the activation temperature. Steam activation can also be used and is typically performed at lower temperatures than C(1 ⁇ 4 activation (800°C to 1100"C). After the activation step an activated carbon powder as heteroatom-doped activated carbon is obtained (112).
  • 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.
  • N -doped carbon we have used urea as an N- source and found moderate solubility (8.5 wt. % ) in furfuryl alcohol at room temperature.
  • 3 gm of urea powder (103) was dissolved into 30 ml of furfuryl alcohol at room temperature (106).
  • 7 gm of maleic acid (102) was added and stirred (107) into solution a room temperature.
  • the solution started darkening in color signifying the onset of the polymerization reaction (108).
  • 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.
  • cross-linking agents like furfural are added to the furfuryl- alcohol/urea polymerizing- catalyst solution described in the previous 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 mi). Urea is however highly soluble in water - with about 108 gm of urea dissolving in 100 ml of water at 20"C (Stumpe, et. al., 2007).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • dimethyldichlorosilane (C 2 H 6 CI 2 S1) was used as the
  • Hexamethylenetetramine (C 6 H 12 N 4 ) was also evaluated as a potential N-source.
  • the solubility limit of C 6 H 12 N 4 in furfuryl alcohol was found to be 26 gm in 100 cc, at room temperature. 4 gm of C 6 H 12 N 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.
  • the carbon source materials used to make our N-doped carbons include furfuryl alcohol, furfural, 2-a.cetylfuran, 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.
  • urea is insoluble in furfural and acetylfuran.
  • An 11.9M solution of urea in water was found to be imm scible in acetylfuran and furfural at room temperature. When heated to 120°C, furfural and the urea solution were still not miscible.
  • furfuryl alcohol may be added to the furfural/urea/water solution at room temperature, to dissolve the urea/water solution.
  • 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 0.45gm 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.
  • 15 cc of a 1: 1 immiscible mixture of furfural and 11.9M urea solution in water was added to 30cc of furfuryl alcohol.
  • 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.
  • 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).
  • 20 cc of acetylfuran was mixed with 12 cc of an 11.9M urea solution (in water). On mixing, a whitish residue was created.
  • 20 cc of furfural was added to the mixture and resulted in a clear solution.
  • 2 gm of oxalic acid was added to the solution and dissolved by stirring at room temperature.
  • 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.
  • the carbon is heated to temperatures between 900°C and 1200°C under a C0 2 atmosphere. Steam activation can also be used and is typically performed at lower temperatures than C0 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.
  • the process described here can also be used to make N and B co-doped carbons.
  • 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.
  • the material was directly subjected to a 200°C treatment, under air, until the rate of weight loss was negligible.
  • 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, CA). Carbonization was done at 600°C, under nitrogen.
  • 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. C0 2 flowing at 3.4 liters/minute, was used to activate the carbon, until 23% weight loss was obtained (77 yield).
  • ICP-MS Inductively Coupled Plasma Mass Spectrometry
  • C-NERGY SUPER C45 carbon black
  • citric acid 251275, Sigma Aldrich, St. Louis, MO
  • 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.
  • 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 (US application 15255128).
  • This process involved immersing the carbonized material into a solution of NaN0 3 in water and alcohol, followed by heat treatments and washing. Accordingly, a solution of 25 gm of NaN0 3 (Lab-Pro ZS0655, Sunnyvale, CA) 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 NaN0 3 treatment. Next, the material was activated in a quartz tube furnace at 950°C with C0 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • oxalic acid 75688, anhydrous, >99.0%, Sigma- Aldrich, St. Louis, MO
  • C-NERGY SUPER C45 carbon black
  • 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 NaN0 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.
  • the carbon was thoroughly washed by boiling in de-ionized water and rinsing several times to remove any remaining NaN0 3 or related by-products.
  • the carbon was then further activated using C0 2 . This was done at 950°C, in a quartz tube furnace with C0 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 C0 2 activation step.
  • FIG. 1 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.
  • 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 air - until 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.
  • the polymerized material was carbonized at 600°C for 60 mins under nitrogen, followed by C0 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.
  • the B-source used here i.e. Boric acid
  • the furfuryl-functional-group containing liquid starting materials a combination of furfural and furfuryl alcohol, in this case
  • This solid material was then heated at 78°C, 120°C, and 2Q0°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.
  • 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 C0 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).
  • 14 gm of urea (U5378, Sigma Aldrich, St. Louis. MO) was added and stirred for 1 hour to dissolve it.
  • 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.
  • the polymerized solid was then carbonized by heating it to 600°C under nitrogen.
  • EXAMPLE 7 [0072] 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.
  • 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 Figure 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,
  • TABLE 8 Properties of N-doped and B-doped carbon used for asymmetric EDLC devices.
  • N-doped carbons shown in table 1
  • the measured surface areas are typically low.
  • 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.
  • 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 devi described in examples 6 and 7 of the instan application.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne un procédé de fabrication de charbon actif dopé par hétéroatomes. Plus particulièrement, l'invention concerne un procédé qui utilise des composés de groupe fonctionnel furfurylique liquides en tant que matières premières, qui sont ensuite utilisés pour dissoudre les composés source contenant des hétéroatomes, avant d'être polymérisés en solides à l'aide de catalyseurs. Les solides polymérisés sont ensuite carbonisés et activés pour obtenir le charbon actif dopé par hétéroatomes. Des condensateurs à double couche électriques (EDLC) ont été fabriqués avec des charbons actifs dopés avec du bore et de l'azote, et testés en termes de performances. En outre, la teneur en bore et en azote dans les charbons actifs a été confirmée par analyse chimique.
PCT/US2017/051944 2016-08-19 2017-09-17 Procédé de fabrication de charbon actif dopé par hétéroatomes Ceased WO2018067292A1 (fr)

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Application Number Priority Date Filing Date Title
US15/242,113 US9938152B2 (en) 2014-07-25 2016-08-19 Method of making activated nano-porous carbon
US15/242,113 2016-08-19
US15/255,128 2016-09-01
US15/255,128 US9975778B2 (en) 2014-07-25 2016-09-01 Method of making chemically activated carbon
US201662396171P 2016-09-18 2016-09-18
US62/396,171 2016-09-18

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CN110652978A (zh) * 2019-08-27 2020-01-07 浙江理工大学 一种非金属改性碳纤维的制备方法及其应用
CN111056547A (zh) * 2019-12-10 2020-04-24 同济大学 一种杂原子掺杂空心碳纳米管的制备方法
CN111774086A (zh) * 2020-07-11 2020-10-16 湘潭大学 一种共价有机框架材料衍生杂原子共掺杂碳纳米片非金属加氢催化剂的制备方法及应用
CN112537770A (zh) * 2020-12-07 2021-03-23 齐鲁工业大学 一种氮掺杂二维碳纳米片的制备方法
US11235978B2 (en) 2018-06-29 2022-02-01 Toyo Tanso Co., Ltd. Method of producing porous carbon, and electrode and catalyst carrier containing porous carbon produced by the method
CN114914101A (zh) * 2022-06-07 2022-08-16 西南交通大学 一种多孔碳储能材料及其制备方法
CN115036152A (zh) * 2022-07-09 2022-09-09 电子科技大学 一种空心球状硼碳氮材料及其制备方法
CN118698501A (zh) * 2024-08-05 2024-09-27 北京市科学技术研究院城市安全与环境科学研究所 改性介孔生物炭吸附剂及其制备方法和应用

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US11702344B2 (en) 2018-06-29 2023-07-18 Toyo Tanso Co., Ltd. Method of producing porous carbon, and electrode and catalyst carrier containing porous carbon produced by the method
US11235978B2 (en) 2018-06-29 2022-02-01 Toyo Tanso Co., Ltd. Method of producing porous carbon, and electrode and catalyst carrier containing porous carbon produced by the method
CN109626374A (zh) * 2019-01-22 2019-04-16 天津大学 一种氮氧双掺杂分级多孔碳材料的制备方法
CN110652978B (zh) * 2019-08-27 2023-05-12 浙江理工大学象山针织研究院有限公司 一种非金属改性碳纤维的制备方法及其应用
CN110652978A (zh) * 2019-08-27 2020-01-07 浙江理工大学 一种非金属改性碳纤维的制备方法及其应用
CN111056547A (zh) * 2019-12-10 2020-04-24 同济大学 一种杂原子掺杂空心碳纳米管的制备方法
CN111774086A (zh) * 2020-07-11 2020-10-16 湘潭大学 一种共价有机框架材料衍生杂原子共掺杂碳纳米片非金属加氢催化剂的制备方法及应用
CN111774086B (zh) * 2020-07-11 2022-09-02 湘潭大学 一种共价有机框架材料衍生杂原子共掺杂碳纳米片非金属加氢催化剂的制备方法及应用
CN112537770A (zh) * 2020-12-07 2021-03-23 齐鲁工业大学 一种氮掺杂二维碳纳米片的制备方法
CN114914101A (zh) * 2022-06-07 2022-08-16 西南交通大学 一种多孔碳储能材料及其制备方法
CN114914101B (zh) * 2022-06-07 2023-05-16 西南交通大学 一种多孔碳储能材料及其制备方法
CN115036152A (zh) * 2022-07-09 2022-09-09 电子科技大学 一种空心球状硼碳氮材料及其制备方法
CN118698501A (zh) * 2024-08-05 2024-09-27 北京市科学技术研究院城市安全与环境科学研究所 改性介孔生物炭吸附剂及其制备方法和应用

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