• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Procedure for the preparation of graphite nanofibers from biogas. The present invention relates to the production of nano-sized synthetic graphite fibers from a carbon material of renewable origin which is obtained together with a hydrogen-rich fuel gas in the biogas revaluation process by catalytic decomposition. This material that is constituted by carbon nanofilaments is progressively transformed into nanofibers with a graphite-like structure by thermal treatment in an inert atmosphere at temperatures equal to or higher than 2400º c, due, in part, to the presence of metallic residues that catalyze the process. These synthesized carbon materials have a high added value and numerous applications, including their use as an anode in lithium-ion batteries, fundamental components of electronic devices, such as mobile phones or laptops. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2540005A1
    申请号:ES201331057
    申请日:2013-07-11
    公开日:2015-07-07
    发明作者:Ignacio CAMEÁN MARTÍNEZ；Nuria CUESTA PEDRAYES；Saúl DE LLOBET CUCALÓN；Ana Beatriz GARCÍA SUÁREZ；Rafael Moliner Álvarez；José Luis PINILLA IBARZ；Alberto RAMOS ALONSO；Isabel Suelves Laiglesia
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    DESCRIPTION
    PREPARATION PROCEDURE FOR GRAPHITE NANOFIBERS FROM BIOGAS
    SECTOR AND OBJECT OF THE INVENTION
    The process object of the present invention falls within the sector of the development of new materials and their applications.

    An object of the present invention is a process for the preparation of 5 nanofibres of graphite comprising a stage of catalytic decomposition of a biogas composed of methane and carbon dioxide at a temperature between 500 ° C and 800 ° C to obtain carbon bionanofilaments, then subjected The carbon bionanofilaments heat treated in an inert atmosphere following a heating program to a final temperature between 2400ºC and 3000ºC to obtain graphite nanofibers.

    Also objects of the present invention are graphite nanofibers obtained by means of the aforementioned process, as well as the use thereof as active materials in rechargeable lithium-ion battery anodes. fifteen

    STATE OF THE TECHNIQUE
    Carbon nanofibers (NFCs) have diameters <100 nm and are formed by sheets of graphene stacked in different ways: perpendicular, parallel or inclined with respect to the fiber axis, depending on the method of preparation and conditions. Among them, the production of NFCs by chemical vapor deposition, using CO and different hydrocarbons, on transition metal catalysts, such as Fe, Co or Ni, has been widely studied, even from the point of view of their commercialization. On a large scale, since in the 1970s (SD Robertson, Carbon 8, 365-368, 1970) the formation of carbon materials with different structures on the catalyst surface was observed during the catalytic decomposition of methane (DCM ). Specifically, the development and tuning of the DCM for the simultaneous production of NFCs and CO2-free hydrogen has been the objective of numerous research papers (Y. Li et al., Catalysis Today 162, 1-48, 2011) and patents (Suelves et al., ES2345805).
     30
    NFCs from DCM have relatively high thermal and electrical conductivities compared to other carbon materials. These properties together with the nanometric size and mesoporous character make them materials
    Suitable for very diverse applications. However, in general, different post-production treatments of the NFCs are necessary to optimize their properties with a view to their subsequent use, including high temperature heat treatment (> 2000 ° C) that increases the graphite three-dimensional structural arrangement and electrical conductivity, while reducing the active centers on the surface, obtaining, in some cases, materials similar to synthetic graphite produced in the industry from petroleum products (A. Ramos et al., Carbon 59, 2-32, 2013). The graphitization of NFCs from the DCM in a fluid bed reactor, using Ni catalysts doped with Cu and supported on SiO2, Al2O3, TiO2 or MgO, has been studied by García et al. (Carbon 47, 2563-79, 2009) and Caméan et al. (Carbon 50, 5387-94, 2012). For this, the 10 NFCs were treated in an electric graphite furnace in the temperature range 1800-2800 ° C for 1 h and in argon flow. Materials prepared from NFCs were characterized, among other techniques, by X-ray Diffraction (DRX), Raman Spectroscopy and Transmission Electron Microscopy (MET). In addition, the influence of both the treatment temperature of the NFCs and the 15 metallic species present (Ni, Si, Ti, Al, Mg from the catalyst used in the DCM) was studied. The analysis of the results of these works clearly showed that metallic species catalyze the process of graffiti of NFCs, so that graphite materials with nanofiber morphology (graphite nanofibers) and crystalline and textural parameters in the range of synthetic graphite were prepared of micrometer size that is used in commercial lithium-ion batteries. These graphite nanofibers were used as anodes in lithium-ion batteries, showing excellent performance, both in terms of the load capacity provided and the retention of said capacity during cycling ( 320 mAhg-1 after 50 cycles of download-upload). In addition, it was concluded that these types of materials are especially suitable for working at high current intensities due to their nanometric size that facilitates the diffusion of lithium ions in their structure (Cameán et al., Journal of Power Sources 198, 303- 7, 2012).

    However, despite the quality and performance of the graphite nanofibers prepared from the NFCs produced in the DCM, it is necessary to consider that methane comes from natural gas (90-95% CH4) which is a fossil fuel and Therefore, a non-renewable energy source. Taking these considerations into account, these NFCs were replaced by others from the catalytic decomposition of biogas, called BNFCs carbon nanofibers. Therefore, the fundamental objective of this invention is to produce synthetic graphite fibers of nanometric size (graphite nanofibers, NFGs) and with suitable properties in terms of structure, texture and electrical conductivity to be used as
    anodes in lithium-ion batteries and / or other energy storage devices, starting from BNFCs and by treatment at temperatures above 2000 ° C.

    The process of catalytic decomposition of biogas for the simultaneous production of carbon nanofibers (BNFCs) and synthesis gas has been investigated by S. de Llobet et al. 5 (International Journal of Hydrogen Energy 37, 7067-7076, 2012) and Pinilla et al. (Fuel 90, 2245-2253, 2011), using Ni catalysts. In this process you can use different mixtures CH4: CO2 (60:40, 50:50 and 70:30 by volume) that simulate the possible concentrations in the biogas and various types of reactors (fixed, rotary, fluidized bed), as well as temperature range, obtaining BNFCs accordingly with 10 very different structural characteristics. The main novelty of this procedure is the use of biogas as a starting material without any purification step being necessary to remove the CO2, and this is in fact the fundamental difference with the patent of Tada et al. (US2006 / 0257310) which have developed a process for the production of carbon and hydrogen nanomaterials from methane, and suggest the possibility of using methane from the purification of biogas, that is, methane with small amounts (0.05 -10% by volume) of CO2. It would be of interest, therefore, to have a process for the preparation of graphite nanofibers using carbon nanofibers as a precursor, obtained in turn from a biogas without the need to reduce the CO2 content present therein. twenty

    DESCRIPTION OF THE INVENTION
    A first object of the present invention is a process for preparing graphite nanofibers from biogas without modifying its original composition with proportions by volume of methane and carbon dioxide comprised between 40% and 80% for methane and between 60% and 20% for carbon dioxide and comprising the following stages:
    a) a first stage of catalytic thermal decomposition of biogas in a temperature range between 500 ° C and 800 ° C, for a period of at least one hour to obtain carbon bionanofilaments; 30
    b) a second stage in which the carbon bionanonofilaments are subjected to heat treatment, atmospheric pressure and in a flow of inert gas following a heating program up to a final temperature between 2400ºC and 3000ºC, which is maintained for a period of time between 30 min and 4 hours. 35

    In a preferred embodiment, the biogas decomposition step is carried out in the presence of a metal catalyst that is selected from Ni, Co, Fe, Mo, Cu and Pd, supported on materials selected from Al2O3, SiO2, TiO2 and MgO and particularly preferred is that
    The catalyst is Ni supported on Al2O3 with a molar ratio Ni: Al between 5 0.17: 3.33 and 1.53: 0.37.

    In a particular embodiment of the process the catalyst is Ni supported on Al2O3 with a Ni: Al molar ratio of 2: 1, prepared by the fusion method and reduced with a hydrogen stream at 550 ° C for 1h before use. 10

    In all the described embodiments of the catalytic decomposition stage, the biogas preferably has a CH4: CO2 composition with a volume ratio that is selected between 60:40 and 50:50 and is fed using a spatial velocity between 3 and 120 LNh-1g-1. fifteen

    Within the indicated temperature range, the catalytic decomposition of biogas is carried out in particular embodiments of the process at a temperature of 600 ° C or at a temperature of 700 ° C.
     twenty
    As for the stage of heat treatment of carbon bionanofilaments, the gas constituting the inert atmosphere is Ar and the heating program comprises the following ramps:
    - 50 ° C. Min-1 in the range from the initial temperature to 700 ° C;
    - 100 ° C. Min-1 in the range from 700 ° C to 1000 ° C; 25
    - 25 ° C. Min-1 in the range from 1000 ° C to 2000 ° C;
    and, finally, 10 ° C. min-1 in the range from 2000 ° C to the final temperature between 2400 ° C and 3000 ° C.

    The final temperature in various particular embodiments of the process is set at 30 2400 ° C, 2500 ° C, 2600 ° C, 2700 ° C, 2800 ° C or 2900 ° C, said final temperature being maintained for a period of 1 hour.

    Optionally, after the catalytic decomposition stage of biogas and before heat treatment in an inert atmosphere, silica powder is added to the carbon bionanofilaments 35
    until reaching an atomic relationship between Si and Ni between 1 and 7, preferably with mechanical agitation to achieve homogeneous mixtures.

    Another object of the present invention is graphite nanofibers obtained by the procedure described above. Said graphite nanofibers have: 5
    - spacing between planes (d002) between 0.3354 and 0.3410 nm;
    - average microcrystalline sizes between 6 and 70 nm in the c axis (Lc);
    - average microcrystalline sizes between 10 and 100 nm on the a (La) axis;

    Finally, it is also another object of the present invention to use said 10 graphite nanofibers as active materials in rechargeable lithium-ion battery anodes.

    BRIEF DESCRIPTION OF THE FIGURES
    Figure 1: SEM image of BNFCs
    Figure 2: SEM image of graphite nanofibers NFG-6-7 / 2800 15
    Figure 3: Discharge capacity vs. number of cycles, at different current intensities, of graphite nanofibers NFG-6-7 / 2800
    Figure 4: Discharge capacity vs. number of cycles, at different current intensities, of a commercial graphite at micrometric size.
     twenty
    MODE OF EMBODIMENT OF THE INVENTION
    Example 1. Production of carbon bio-nanofibers (BNFCs)
    BNFCs are obtained by catalytic decomposition of biogas in a rotating bed reactor heated in an electric furnace. Specifically, in this example, a mixture CH4: CO2 with a volume ratio of 60:40 and a nickel catalyst supported on alumina with a Ni: Al molar ratio of 2: 1 that had been prepared by the method was used melting and reduced with a stream of hydrogen at 550 ° C for 1 h before use. The biogas decomposition experiments were carried out at two temperatures, 600 ° C and 700 ° C, using a space velocity of 30 LNh-1g-1. The BNFCs obtained in these experiments were named by adding the number 6 by 600 ° C or 7 by 30 700 ° C to the general acronym BNFC, namely BNFC-6 and BNFC-7. The production (gram of carbon per gram of catalyst per hour, gC · gCat-1 · h-1) and the elementary analysis of these materials are given in Table 1. The carbon, nitrogen and hydrogen contents in BNFCs are determined by total oxidation of the sample and subsequent detection in an analyzer, while the nickel and aluminum elements that come from the catalyst are analyzed by mass ICP.


    Table 1. Production and elementary analysis (% weight) of BNFCs obtained by catalytic decomposition of biogas (CH4: CO2 ratio v: v 60:40)
     BNFCs  Production (gC · gcat-1 · h-1) C (%) N (%) H (%) Ni (%) Al (%)
     BNFC-6  2.0 91.11 0.11 0.16 3.70 1.43
     BNFC-7  1.9 89.25 0.15 0.10 3.83 1.07
     5
    BNFCs that are mainly made of carbon are deposited on the catalyst in the form of nanofilaments a few microns in length; consequently, they contain metal particles some of which are located at their ends, as can be seen in the image obtained by SEM electron microscopy of Figure 1. In addition, the presence of heterogeneously distributed metal residues 10 between the nanofilaments of carbon.

    Example 2. Production of graphite nanofibers (NFGs)
    The production of NFGs is carried out by heat treatment of the BNFCs obtained as a co-product in the catalytic decomposition of biogas (see Example 1) in a three-phase electric furnace with a graphite resistor, provided with a controller / programmer and a external cooling system that feeds the water jackets of the heating chamber and electrical contacts, keeping the temperature of the chamber below 35 ºC. The temperature measurement is carried out by means of a K / Ni type Cr thermocouple located in the central zone of the heating chamber, and an optical pyrometer capable of measuring temperatures up to 3000 ° C through a graphite tube that crosses the wall of the oven at the same height as the thermocouple. When the oven reaches 950 ° C, the thermocouple is automatically removed from the inside of the heating chamber, at the same time that the pyrometer starts operating. In a type experiment, the sample is deposited in a cylindrical graphite sample holder that is introduced into the oven, which is hermetically sealed by an anchoring system. Then and as a previous step to heat treatment, the furnace is purged by successive vacuum / Ar flow cycles in order to guarantee the absence of oxygen inside. BNFCs were treated in Ar flow (2 lmin-1) at temperatures of 2600 ºC and 2800 ºC for 1 h, using the following heating ramps: 50 ºC min-30 1 in the range 0-700 ºC; 100 ° C-1 in the range 700-1000 ° C; 25 ° C-1 in the range 1000-2000 ° C; and, finally, 10 ° C-1 in the range 2000-2600 ° C or 2800 ° C. The NFGs
    obtained were named from the corresponding BNFC by adding the treatment temperature. For example, NFG-6/2800 are graphite nanofibers obtained from BNFC-6 by treatment at 2800 ° C under the conditions mentioned above.

    In addition to the BNFCs directly produced in the catalytic decomposition of biogas 5 (BNFC-6 and BNFC-7), others were prepared from them by adding different amounts of silica powder (up to Si / Ni atomic ratios in the nanofiber of 1, 5 and 7) followed by mechanical agitation to achieve homogeneous mixtures. These new BNFCs, named by adding said Si / Ni ratio to the original nanofiber (for example, BNFC-6-1 is that prepared from BNFC-6 by adding silica to a Si / Ni ratio of 1) were also heat treated at 2800 ° C, under the conditions described above, to prepare NFGs.

    Example 3. Evaluation of the quality of graphite nanofibers (NFGs)
    The NFGs prepared from the BNFCs were characterized by 15 X-ray diffraction (DRX) and the crystalline parameters were determined: distance between planes, d002, and crystal sizes in the direction of the axes, perpendicular, Lc, and basal , The. The diffractograms from which these parameters were calculated were obtained in a device with a monochromatic CuKα X-ray tube, a Göbel mirror and a parallel radiation detector. Samples were prepared by the powder method using a glass sample holder. The conditions of the equipment in which the diffractograms have been obtained are shown in Table 2. For each material, three measurements were made, each of them from a different and representative portion of the sample, which has allowed us to obtain values precise of the crystalline parameters and determine the error in calculating them. The width of the peak at half the height, β, has been corrected to discount the proper widening of the apparatus according to the expression:
     22bB

    To do this, obtaining the diffractogram under a pure and well crystallized reference substance, in this case Yes, allows the correction of the experimental width of the signals, which was evaluated at 0.16 °.
    Table 2. Measurement parameters used for DRX analysis of materials
     Parameter  Value
     Intensity  40 mA
     Voltage  40 kV
     Step size  0.02 º
     Passing time  3 s
     Initial position  5th
     Final position  90 º
     Type Detector  Scintillation

    The distance between two crystallographic planes of the family of planes (002), d002, has been calculated using Bragg's law that sets the geometric conditions necessary for X-ray diffraction in crystals to occur:
     0020022send

    The sizes of the crystals in the direction of the axis c, Lc, and in the direction of the basal plane, La, have been obtained from the following equations:
               ) cos (0029.0cL) cos (11084.1aL

     = Bragg diffraction angle of the peaks (002) and (110) expressed in radians
     = wavelength
     = width at half height of the peak expressed in radians 15

    The degree of structural order of a given material, and consequently the quality and possible applications, is estimated based on the values of the crystalline parameters. As the bi-three-dimensional arrangement of the aromatic sheets improves, the distance between planes, d002, decreases, being able to reach a minimum value of 0.3354 nm that corresponds to the theoretical value of the graphite monocrystalline. At the same time, the crystal grows both in the direction of the basal plane, La, and in the direction of the normal plane, Lc. The crystalline parameters of the prepared NFGs and the BNFCs used as starting materials are given in Table 3.
     25
    Table 3. Crystal parameters (d002, Lc, La) of BNFCs (BNFC-6 and BNFC-7) and NFGs prepared by heat treatment
     Material  d002 (nm) Lc (nm) La (nm)
     BNFC-6  0.3417 6.0 15.5
     NFG-6/2600  0.3410 9.3 25.4
     NFG-6/2800  0.3407 9.8 26.5
     NFG-6-1 / 2800  0.3399 10.1 34.2
     NFG-6-5 / 2800  0.3380 14.9 51.3
     NFG-6-7 / 2800  0.3370 21.6 55.9
     BNFC-7  0.3424 5.7 13.7
     NFG-7/2600  0.3423 6.7 22.4
     NFG-7/2800  0.3420 7.1 26.4
     NFG-7-1 / 2800  0.3402 9.3 41.0
     NFG-7-5 / 2800  0.3367 25.1 57.3
     NFG-7-7 / 2800  0.3364 31.1 62.9

    Prepared NFGs have a high degree of three-dimensional structural order, especially those obtained from BNFCs with higher 5 Si / Ni atomic ratios, for example NFG-7-7 / 2800, due to the catalytic effect of these elements on graffiti of carbon materials. In general, as can be seen from the structure of the nanofilaments in Figure 2, high-quality NFGs have been prepared and that, in addition, have crystalline parameters totally comparable to commercial synthetic micrometric graphite graphites, produced from derivatives of the oil, and that 10 are being used for very different industrial applications from electrodes for the steel and aluminum industries to anodes in commercial lithium-ion batteries or components in fuel cells for hydrogen production.

    Example 4. Application of graphite nanofibers (NFGs) as anode in lithium-ion batteries
    First of all, the preparation of the working electrode is carried out. For this, 80 mg of NFG (active material) is mixed with 20 mg of a polymer that acts as a binder, in this case Polyvinylidene Fluoride (PVDF), and a few drops of an organic solvent are added to the mixture, in this case 1-methyl-2-pyrrolidone, to form a suspension which, then, extends over the surface of a Cu sheet 25 μm thick and 12 mm in diameter previously weighed. The copper foil coated with a thin layer of the suspension is dried in an oven at 120 ° C and vacuum for at least 2 hours, in order to
    remove the solvent. Once dry, a pressure of 1t is applied with a hydraulic press and then weighed to determine by difference the amount of active material.
    The working electrode formed by the NFG / PVDF composite material on the copper foil is electrochemically characterized using a two-electrode Swagelok laboratory cell, working electrode and counter-electrode, the assembly of which is carried out inside a single glove box in which the H2O and O2 levels are below 0.1 ppm, and whose working gas is Ar. This cell model consists of two straight-fitting Teflon outer fittings inside which the working electrode, two 12 mm diameter glass fibers impregnated with the electrolyte and the counter electrode are arranged. The electrolyte is a 1M solution of LiPF6 in a 1: 1 by weight mixture of 10 ethylene carbonate (EC) and diethyl carbonate (DEC) and the counter electrode is a 12 mm diameter lithium tablet. At the ends of each fitting a stainless steel manifold is placed that allows the passage of electric current. The cells thus assembled that have an initial voltage of 3-3.3 V are connected to a potentiostat / galvanostat and subjected to galvanostatic cycles (successive cycles of discharge-charge at constant current intensity), at 15 different current densities, between voltages 2.1 V-0.003 V to complete 50 cycles.

    Figure 3 shows, as an example, the discharge capacity, at current densities in the range 18.6-744.0 mAg-1, of the cell in which it has been used as active material in the electrode of I work the graphite nanofiber called NFG-6-7 / 2800 (see Table 3 and Figure 2).

    Graphite nanofibers NFG-6-7 / 2800 have good cyclability (retention of discharge capacity throughout cycling), even at high current densities. In addition, the discharge capacities provided by these NFGs are comparable and even higher (at current densities> 100 mAg-1) than those corresponding to a synthetic graphite of micrometric size used as an anode in commercial lithium-ion batteries (Figure 4 ). The nanometric size of the NFGs favors the diffusion of lithium ions in their structure and as the current density increases, that is, the charge-discharge rate of the cell, this positive effect is more noticeable.
    权利要求:
    Claims (20)
    [1]
    1. Procedure for preparing graphite nanofibers from biogas comprising the following stages:
    a) a first stage of catalytic thermal decomposition of biogas in a temperature range between 500 ° C and 800 ° C, for a period of at least 5 hours to obtain carbon bionanofilaments;
    b) a second stage in which the carbon bionanonofilaments are subjected to heat treatment, atmospheric pressure and in a flow of inert gas following a heating program up to a final temperature between 2400ºC and 3000ºC, which is maintained for a period of time between 30 min 10 and 4 hours;
    characterized in that the process starts from biogas without modifying its original composition with proportions in volume of methane and carbon dioxide comprised between 40% and 80% for methane and between 60% and 20% for carbon dioxide.
     fifteen
    [2]
    2. The method according to claim 1, characterized in that the biogas decomposition step is carried out in the presence of a metal catalyst selected from Ni, Co, Fe, Mo, Cu and Pd, supported on materials selected from Al2O3, SiO2, TiO2 and MgO.
     twenty
    [3]
    3. Method according to claim 2, characterized in that the catalyst is Ni supported on Al2O3 with a molar ratio Ni: Al between 0.17: 3.33 and 1.53: 0.37.

    [4]
    4. Method according to claim 3, characterized in that the catalyst is Ni 25 supported on Al2O3 with a Ni: Al molar ratio of 2: 1, prepared by the melting method and reduced with a hydrogen current at 550 ° C for 1h before utilization.

    [5]
    5. Method according to any one of claims 1 to 4, characterized in that in the catalytic decomposition step the biogas has a CH4: CO2 composition with a volume ratio that is selected between 60:40 and 50:50 and is fed using a space velocity between 3 and 120 LNh-1g-1.

    [6]
    Method according to any one of claims 1 to 5, characterized in that the catalytic decomposition step of the biogas is carried out at a temperature of 600 ° C. 35

    [7]
    7. Method according to any one of claims 1 to 5, characterized in that the catalytic decomposition step of the biogas is carried out at a temperature of 700 ° C.

    [8]
    Method according to any one of claims 1 to 7, characterized in that in the heat treatment stage of the carbon bionanofilaments the gas that constitutes the inert atmosphere is Ar.

    [9]
    9. Method according to claim 8, characterized in that the heating program comprises the following ramps:
    - 50 ° C. Min-1 in the range from the initial temperature to 700 ° C; 10
    - 100 ° C. Min-1 in the range from 700 ° C to 1000 ° C;
    - 25 ° C. Min-1 in the range from 1000 ° C to 2000 ° C;
    and, finally, 10 ° C. min-1 in the range from 2000 ° C to the final temperature between 2400 ° C and 3000 ° C.
     fifteen
    [10]
    10. Preparation process of graphite nanofibers according to claim 9, characterized in that the final temperature is 2400 ° C.

    [11]
    11. Method according to claim 9, characterized in that the final temperature is 2500 ° C. twenty

    [12]
    12. Method according to claim 9, characterized in that the final temperature is 2600 ° C.

    [13]
    13. Method according to claim 9, characterized in that the final temperature is 25 2700 ° C.

    [14]
    14. Method according to claim 9, characterized in that the final temperature is 2800 ° C.
     30
    [15]
    15. Method according to claim 9, characterized in that the final temperature is 2900 ° C.

    [16]
    16. Method according to any one of claims 9 to 15, characterized in that the final temperature is maintained for a period of 1 hour. 35
    [17]
    17. Method according to any one of claims 1 to 16, characterized in that after the catalytic decomposition stage of biogas and before the inert atmosphere heat treatment, silica powder is added to the carbon bionanofilaments until an atomic relationship between Si and Ni is reached. between 1 and 7.
     5
    [18]
    18. Method according to claim 17, characterized in that the silica is added with mechanical stirring to achieve homogeneous mixtures.

    [19]
    19. Graphite nanofibers obtained by a process according to claims 1 to 18, characterized in that they have:
    - spacing between planes (d002) between 0.3354 and 0.3410 nm;
    - average microcrystalline sizes between 6 and 70 nm in the c axis (Lc);
    - average microcrystalline sizes between 10 and 100 nm on the a (La) axis;

    [20]
    20. Use of graphite nanofibers according to claim 19 as active materials in 15 anodes of rechargeable lithium-ion batteries.
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    同族专利:
    公开号 | 公开日
    EP3045575A4|2017-01-18|
    ES2540005B1|2016-04-13|
    EP3045575A1|2016-07-20|
    WO2015004295A1|2015-01-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    KR20090131782A|2008-06-19|2009-12-30|주식회사 나노솔루션|Composition method for carbonnanotube or carbon nanofiber using bio-mass|
    JP4697941B2|2005-05-11|2011-06-08|株式会社日本製鋼所|Method for producing functional nanocarbon and hydrogen by direct decomposition of lower hydrocarbons|
    ES2345805B1|2009-03-31|2011-07-22|Consejo Superior De Investigaciones Científicas |IRON CATALYSTS FOR THE SIMULTANEOUS PRODUCTION OF HYDROGEN AND CARBON NANOFILAMENTS BY METAL CATALYTIC DECOMPOSITION.|ES2717199A1|2017-12-19|2019-06-19|Pamies Javier Biela|BIOGAS PLANT |
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