WO2005007566A2 - Nanoporous carbide derived carbon with tunable pore size - Google Patents
Nanoporous carbide derived carbon with tunable pore size Download PDFInfo
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- WO2005007566A2 WO2005007566A2 PCT/US2004/021382 US2004021382W WO2005007566A2 WO 2005007566 A2 WO2005007566 A2 WO 2005007566A2 US 2004021382 W US2004021382 W US 2004021382W WO 2005007566 A2 WO2005007566 A2 WO 2005007566A2
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- pore size
- carbide
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- 239000011148 porous material Substances 0.000 title claims abstract description 98
- 229910021401 carbide-derived carbon Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 20
- 229910009817 Ti3SiC2 Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 238000009826 distribution Methods 0.000 description 19
- 239000007789 gas Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 13
- 238000005660 chlorination reaction Methods 0.000 description 12
- 238000000235 small-angle X-ray scattering Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000001247 metal acetylides Chemical class 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000004279 X-ray Guinier Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910003178 Mo2C Inorganic materials 0.000 description 2
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 238000001530 Raman microscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005315 distribution function Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28088—Pore-size distribution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
-
- 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
Definitions
- Porous solids are of great technological importance due to their ability to interact with gases and liquids not only at the surface, but throughout their bulk. While large pores can be produced and well controlled in a variety of materials, nanopores in the range of 2 nm and below (micropores, according to IUPAC classification) are usually achieved only in carbons or zeolites. During the past decades major efforts in the field of porous materials have been directed toward control of the size, shape and uniformity of the pores. Highly crystallized zeolites have a narrow pore size distribution, but discrete pore sizes and the fine-tuning of pore size is impossible in zeolites because pores are controlled by a lattice structure.
- Porous carbons produced by thermal decomposition of organic materials may have pore diameters down to 0.3 nm, or mesopores of several nanometers, but they typically have a broad pore size distribution that limits their ability to separate molecules of different sizes. Materials with a tunable pore structure at the atomic level and a narrow pore size distribution do not exist. Selective etching of carbides is an attractive technique for the synthesis of various carbon structures from nanotubes to diamonds (Derycke et al . 2002 Nano Lett . 2:1043-1046; Gogotsi et al . 2001 Nature 411:283-287). Carbon produced by the extraction of metals from carbides is called carbide-derived carbon (CDC) (Gogotsi, et al .
- CDC carbide-derived carbon
- An object of the present invention is to provide a method of producing a nanoporous carbide-derived carbon composition with a tunable pore structure and a narrow pore size.
- the method of the present invention comprises extracting metals from a carbide using a halogen at elevated temperature to produce a nanoporous carbide- derived carbon composition with a tunable pore structure and a narrow pore size. Pore size is controlled by selection of the carbide and/or the halogen. Tuning of the pore size is achieved by changing the extraction temperature .
- Another object of the present invention is to provide nanoporous carbide-derived carbon compositions produced with or without mesopores. Uses for these compositions include, but are not limited to, molecular sieves, gas storage, catalysts, adsorbents, battery electrodes, supercapacitors, water or air filters, and medical devices.
- Figures la and lb are graphs demonstrating the differential pore size distributions for CDCs produced in accordance with the method of the present invention. As shown, the pore sizes increase with increasing chlorination temperatures .
- Figure 2a, 2b and 2c show data for seven CDC samples produced in accordance with the method of the present invention spanning elevated chlorination temperatures of between 300°C and 1400°C, demonstrating that pore size can be controlled with better than 0.05 nm accuracy.
- Figures 3a and 3b show data from Raman spectroscopy indicating that carbon is formed at 200°C from initial carbide precursors .
- the present invention provides a method of producing a nanoporous carbide-derived carbon (CDC) composition with a tunable pore structure and a narrow pore size.
- a metal carbide is exposed to a halogen so that the metal is extracted from the carbide.
- the inventors have found that this halogen extraction, when performed under elevated temperatures, produces a nanoporous carbide-derived carbon composition with a tunable pore structure and a narrow ranges of pore sizes. Desired pore sizes can be achieved through selection of the halogen and/or the carbide.
- Halogens useful in the present invention include fluorine, chlorine, bromine, and iodine.
- the halogen may be in the form of a gas or liquid.
- halogen gas it is meant to be inclusive of any gas or gas mixture which comprises at least one halogen.
- the halogen gas may contain multiple halogens.
- the halogen is in the form of a chlorine containing gas or a gas mixture containing chlorine and argon (Ar) .
- the pore size can be selected by changing the halogen. The heavier the halogen used, the larger the resulting pores. Likewise, the smallest pores are produced by fluorine, with larger halogens like chlorine, bromine and iodine producing larger pores.
- the carbide used in the present invention may be any suitable carbide.
- suitable carbides include, but are not limited to, SiC, TiC, ZrC, B 4 C, TaC, and Mo 2 C.
- the pore sizes can also be tuned to a selected or desired size.
- both the halogen and the carbide may be chosen to provide a desired pore size.
- the carbide is Ti 3 SiC 2 .
- CDC produced from Ti 3 SiC 2 has a more narrow pore size distribution than single wall carbon nano-tubes or activated carbons, and it has a pore size distribution that is comparable to that of zeolites.
- Ti 3 SiC 2 is available in different forms including powders and bulk samples.
- Ti 3 SiC 2 is a soft ceramic with a lamellar structure which can easily be machined to any shape. Etching of Ti 3 SiC 2 generates a larger pore volume, about 75%, as compared to TiC or SiC which are about 56.2% and 57.3%, respectively.
- the method of the present invention allows tuning the porosity of carbide-derived carbons (CDCs) with sub- Angstrom accuracy in a wide range by controlling the halogen temperature.
- the desired pore size of the composition is achieved by selection of a halogen and of a carbide each for their respective tuning ability. Elevated temperatures for the halogen extraction are then chosen to selectively tune the carbide composition.
- the CDCs of the present invention are produced at elevated temperatures from between 200°C to 1400°C.
- CDCs can be produced as a powder, a coating, a membrane or parts with near final shapes.
- the CDC may be produced with or without mesopores.
- isotherms of CDCs are produced with the presence of mesopores .
- Tunable pore size can be achieved with the method of the present invention with at least 0.05 nm accuracy.
- the inventors have found that chlorination in a flow of pure Cl 2 for 3 hours in a quartz tube furnace results in extraction of Ti and Si from Ti 3 SiC 2 leading to the formation of carbon by the reaction:
- Figure 2 shows data for 7 samples spanning the range between 300°C and 1200°C and demonstrating the dependencies of gyration radius (R g ) and pore size on chlorination temperature.
- Figure 2a shows experimental SAXS curves in Guinier coordinates;
- Figure 2b shows a distribution of gyration radius m(Rg) ,- and
- Figure 2c shows a comparison of pore sizes obtained by CH 3 C1 sorption and SAXS for different chlorination temperatures of Ti 3 SiC 2 .
- No pores with Rg larger than 0.6 nm were detected by SAXS.
- the SAXS-derived Rg at 600°C is 0.53 nm, while the sorption-based D m (average of 500°C and 700°C values) is 0.61 nm. Taking the latter as the height of slit pores, the implied R is 0.71 nm, comparable to the radii of slit-shaped nanopores in polymer-derived materials.
- slit pores have been formed
- Figure 3b demonstrates the temperature dependence of ID/IG ratio and provides TEM images showing evolution of the carbon structure with temperature.
- CDC produced in temperature range I (300°C) is completely amorphous. Slow pore growth occurs in range II. Formation of carbon fringes at 700 °C and higher temperatures show the beginning of the structure ordering leading to increasing pore size and appearance of mesopores in range III. Pronounced graphitization is observed at 1200 °C (range IV) , resulting in a sharper G-band in the Raman spectrum and decreased I d /I g ratio. Ti can be extracted by Cl 2 at lower temperatures than Si.
- Total volume and characteristic dimensions of meso- and nanopores can be controlled by selection of a binary or ternary carbide or a carbide solid solution and variation of the chlorination process parameters.
- carbon derived from SiC at 900 °C has a narrow pore size distribution and an average pore size of 0.65 nm, similar to CDCs produced from Ti 3 SiC at 700 °C, but with no mesopores.
- Carbon made from SiC at 1200 °C had a pore size of 1.2 nm, and SiC and BC derived carbons have values from 0.8 to 2.1 nm.
- the pore volume of CDCs can vary from -50% to -80%.
- CDCs derived from Ti 3 SiC have the theoretical density of 0.55 g/c ⁇ v. CDC samples are hydrophilic and adsorb water quickly; rapidly sinking in water. However, if the surface is sealed with a sealing compound, lacquer, polymer, nail polish or other suitable sealant, they float because their density is well below 1 g/cm 3 . It is notable that CDCs do not have macroporosity if produced from a dense ceramic or a carbide single crystal. However, a controlled amount of macroporosity can be introduced by using sintered porous ceramics.
- CDCs may be used for some applications where single-wall carbon nanotubes are currently considered. For example, CDC is an attractive material for electrodes for electrochemical double- layer capacitors commonly called
- “supercapacitors” because the pore size distribution can be tuned to match various electrolytes. Hydrogen uptake depends on the porous structure of the adsorbent. The highest uptake was achieved in nanoporous carbons with SSA above 1000 m/g and almost no mesopores. CDCs produced at 600 °C and 1100 °C have SSA of 1061 m 2 /g and 1431 m 2 /g, respectively, and SSA of up to 2000 m 2 /g has been measured for SiC- and B 4 C-derived CDC. The ability to tune the pore size to exactly fit the hydrogen (or other gas) molecule is of principal importance for gas storage applications. About 40 wt .
- % Cl 2 is trapped in CDCs produced at 300-400°C at room temperature and ambient pressure, if the cooling is done in argon, and it can reach 55-60 wt . % when cooled in Cl 2 .
- the amount of Cl 2 stored decreases with increasing pore size, reaching less than 5 wt . % at 1200°C.
- the stored chlorine is slowly released, and its amount goes down to approximately 20 wt . % after storage for ten days in open air. Fast release of atomic chlorine is observed upon heating in He up to 600°C at 10°C/minute.
- Example 1 Calculation of Total Pore Volume Total pore volume (V ⁇ )and average pore size were calculated from Ar and CH 3 C1 adsorption isotherms according to HK (Horvath and Kawazoe) theory. Specific surface area, according to BET (Brunauer, Emmet, and Teller) theory and nanopore volume, was calculated using t-plots based on the CH 3 C1 or Ar sorption isotherms. Nitrogen adsorption did not produce reliable results on samples with a pore size smaller than 1 nm.
- Ar adsorption (Micromeretics ASAP Pore Analyzer) was used to measure pore sizes above and under 1 nm, but the technique required long periods of time (5 days) for equilibration and could not produce the full distribution when the pore size approached 0.5 nm.
- the methyl chloride adsorption isotherms were used to measure the pore size below 0.7 nm assuming a slit pore shape.
- Example 2 Small-angle X-ray scattering
- SAXS Small-angle X-ray scattering
- I In (I) vs. Q 2 curves into components corresponding to pores with different Rg, distribution functions of Rg- were found.
- Example 3 Determination of Structure of CDCs Raman microspectroscopy (Renishaw 1000, Ar ion laser, 514.5 nm) , transmission electron microscopy (TEM, JEOL 2010F) , energy-dispersive spectroscopy (EDS) and X-ray diffraction (XRD, Siemens) , were used to study the structure of CDC powders.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2004257183A AU2004257183A1 (en) | 2003-07-03 | 2004-07-02 | Nanoporous carbide derived carbon with tunable pore size |
EP04756600A EP1667932A4 (en) | 2003-07-03 | 2004-07-02 | Nanoporous carbide derived carbon with tunable pore size |
US10/561,768 US8137650B2 (en) | 2003-07-03 | 2004-07-02 | Nanoporous carbide derived carbon with tunable pore size |
CA002530806A CA2530806A1 (en) | 2003-07-03 | 2004-07-02 | Nanoporous carbide derived carbon with tunable pore size |
JP2006518802A JP4646911B2 (en) | 2003-07-03 | 2004-07-02 | Nanoporous carbide-derived carbon with variable pore size |
US13/331,184 US20120093709A1 (en) | 2003-07-03 | 2011-12-20 | Nanoporous carbide derived carbon with tunable pore size |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US48484003P | 2003-07-03 | 2003-07-03 | |
US60/484,840 | 2003-07-03 |
Related Child Applications (1)
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US13/331,184 Continuation US20120093709A1 (en) | 2003-07-03 | 2011-12-20 | Nanoporous carbide derived carbon with tunable pore size |
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Publication Number | Publication Date |
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WO2005007566A2 true WO2005007566A2 (en) | 2005-01-27 |
WO2005007566A3 WO2005007566A3 (en) | 2005-06-30 |
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PCT/US2004/021382 WO2005007566A2 (en) | 2003-07-03 | 2004-07-02 | Nanoporous carbide derived carbon with tunable pore size |
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US (2) | US8137650B2 (en) |
EP (1) | EP1667932A4 (en) |
JP (1) | JP4646911B2 (en) |
AU (1) | AU2004257183A1 (en) |
CA (1) | CA2530806A1 (en) |
WO (1) | WO2005007566A2 (en) |
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EP1916223A1 (en) * | 2006-10-24 | 2008-04-30 | Samsung SDI Co., Ltd. | Method of preparing a carbonaceous material for an emitter of an electron emission device |
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US20110122542A1 (en) * | 2008-01-31 | 2011-05-26 | Drexel University | Supercapacitor compositions, devices and related methods |
DE102010022831A1 (en) * | 2010-02-17 | 2011-08-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 80686 | Double-layer capacitor |
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Also Published As
Publication number | Publication date |
---|---|
WO2005007566A3 (en) | 2005-06-30 |
US20060165584A1 (en) | 2006-07-27 |
JP4646911B2 (en) | 2011-03-09 |
JP2007531678A (en) | 2007-11-08 |
EP1667932A2 (en) | 2006-06-14 |
EP1667932A4 (en) | 2007-10-31 |
US20120093709A1 (en) | 2012-04-19 |
CA2530806A1 (en) | 2005-01-27 |
US8137650B2 (en) | 2012-03-20 |
AU2004257183A1 (en) | 2005-01-27 |
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