Surface-modified carbon hybrid particles, methods of making, and applications of the same.
Abstract
TIM14415PCT 1 ABSTRACT The present disclosure relates to surface-modified carbon hybrid particles in agglomerated form, methods for making such surface-modified carbon hybrid particles and their use, for example as conductive additives. The surface-modified carbon hybrid particles are characterized by a high surface area and a high mesopore content. The disclosure also pertains to methods for making dispersions of such compounds in a liquid medium in the presence of a surfactant and their use as conductive coatings. Polymer compounds filled with the surface-modified carbon hybrid particles are also disclosed. A further disclosure relates to the use of surface-modified carbon hybrid particles as carbon supports.

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14 claims: 7 independent, 7 dependent
- 1CLAIMS REIVINDICACIONES 1. Partículas híbridas de carbono caracterizadas porque comprenden un núcleo de grafito recubiertas con carbono amorfo en forma de aglomerado que tiene un área de superficie BET de al menos 50 m2/g, o al menos 80 m2/g, o al menos 100 m2/g y no mayor que 800 m2/g, y un área de mesoporos DFT de al menos 40 m2/g, o al menos 60 m2/g, o al menos 70 m2/g, o al menos 80 m2/g y no mayor de 400 m2/g, en donde la superficie de dichas partículas híbridas de carbono ha sido modificada mediante oxidación controlada. one. Carbon hybrid particles characterized in that they comprise an agglomerate-shaped amorphous carbon-coated graphite core having a BET surface area of at least 50 m2/ g, or at least 80 m2/ g, or at least 100 m2/ g and not greater than 800 m2/ g, and a DFT mesopore area of at least 40 m2/ g, or at least 60 m2/ g, or at least 70 m2/ g, or at least 80 m2/ g and not greater than 400 m2/ g, where the surface of said hybrid carbon particles has been modified by controlled oxidation.
- 4Las partículas híbridas de carbono de superficie modificada de conformidad con cualquiera de las reivindicaciones 1 a la 3, caracterizadas porque Four. The surface modified carbon hybrid particles according to any of claims 1 to 3, characterized in that (iii) la densidad compactada g/cm3, es de (iii) the compacted density g / cm3, It is 0.35 a 0.7 0.35 to 0.7 0.4 a 0.7 g/cm3;y/o (iv) la densidad Scott es de 0.4 to 0.7 g / cm3;and / or (iv) the Scott density is 0.2 a 0.2 to 0.6 g / cm3, or 0.25 0.6 g/cm3, o 0.25 0.6 g / cm3;0.6 g/cm3;and / or (v) the oil absorption is y/o (v) la absorción de petróleo es de 150% p/p o menos, 150% w / w or less, 140% p/p o menos, o 120% p/p o menos, o 140% w / w or less, or 120% w / w or less, or 100% p/p o menos, o 80% p/p o menos;y/o 100% w / w or less, or 80% w / w or less;me IMPI (vi) en donde el grado de grafitización es de 80 a 95%, o de 85 a 95%, o de 90 a 95%. IMPI (vi) where the degree of graphitization is 80 to 95%, or 85 to 95%, or 90 to 95%.
- 5The surface modified carbon hybrid particles according to any of claims 1 to 4, characterized in that the Dgo value of non-agglomerated particles, as determined by the wet dispersion method, is less than 10 pm, or less than 8 pm, or less than 5 pm, or less than 4 pm, or less than 3 pm, or less than 2 pm, or less than 1.8 pm;and / or where the Dso value of non-agglomerated particles is less than 4 pm, or less than 2 pm, or less than 1 pm, or less than 0.75 pm, or less than 0.4 pm, or less than 0.3 pm;and / or where the Dio value of non-agglomerated particles is less than 0.6 pm, or less than 0.4 pm, or less than 0.2 pm, or less than 0.15 pm. 5. Las partículas híbridas de carbono de superficie modificada de conformidad con cualquiera de las reivindicaciones 1 a la 4, caracterizadas porque el valor Dgo de partículas no aglomeradas, según lo determinado por el método de dispersión en húmedo, es menor que 10 pm, o menos de 8 pm, o menos de 5 pm, o menos de 4 pm, o menos de 3 pm, o menos de 2 pm, o menos de 1.8 pm;y/o en donde el valor Dso de partículas no aglomeradas es menor que 4 pm, o menos de 2 pm, o menos de 1 pm, o menos de 0.75 pm, o menos de 0.4 pm, o menos de 0.3 pm;y/o en donde el valor Dio de partículas no aglomeradas es menor que 0.6 pm, o menos de 0.4 pm, o menos de 0.2 pm, o menos de 0.15 pm.
- 6A method of manufacturing surface modified carbon hybrid particles as defined in any one of claims 1 to 5, characterized in that it comprises the steps of:6. Un método de fabricación de partículas híbridas de carbono de superficie modificada como se define en cualquiera de conformidad con las reivindicaciones 1 a la 5, caracterizado porque comprende los pasos de: a) grinding graphite in a gas-tight sealed mill;and a) molienda de grafito en un molino sellado hermético al gas;y b) funcionalización del carbono híbrido resultante por oxidación controlada;b) functionalization of the resulting hybrid carbon by controlled oxidation;en donde el método además incluy mantener el producto del paso de molienda a) en el molino para permitir la where the method also included keeping the product of the grinding step a) in the mill to allow the IMPI terminación de la aglomeración de las partículas primarias molidas antes de su funcionalización;IMPI termination of the agglomeration of the ground primary particles before their functionalization;preferably where step a) is carried out until the Dgo value of non-agglomerated particles as determined by the wet dispersion method is less preferiblemente en donde el paso a) se lleva a cabo hasta que el valor Dgo de partículas no aglomeradas tal como se determina por el método de dispersión en húmedo es menos less than 0.6 pm, or less than 0.4 pm, or less than 0.2 pm, or less than 0.15 pm menor que 0.6 pm, o menos de 0.4 pm, o menos de 0.2 pm, o menos de 0.15 pm
- 9The method according to any of claims 6 to 8, wherein the product obtained from step b) is dispersed in a liquid in the presence of a surfactant or a polymeric compound by applying shear force to deagglomerate the particles. 9. El método de conformidad con cualquier de las reivindicaciones 6 a la 8, en donde el producto obtenido del paso b) se dispersa en un líquido en presencia de un tensioactivo o un compuesto polimérico mediante la aplicación de fuerza de cizallamiento para desaglomerar las partículas.
- 10The surface modified carbon hybrid particles according to any of claims 1 to 5, obtainable by the method as defined in any of claims 6 to 9. 10. Las partículas híbridas de carbono de superficie modificada de conformidad con cualquiera de las reivindicaciones 1 a la 5, obtenibles por el método como se define en cualquiera de las reivindicaciones 6 a la 9.
- 12A polymer compound filled with the particles 12. Un compuesto de polímero lleno de las partículas o la reivindicación 10 como un aditivo conductor;or claim 10 as a conductive additive;preferably where barium sulfate is added preferiblemente en donde el sulfato de bario se añade according to claim 11 as a conductive additive;conformidad con la reivindicación 11 como un aditivo conductor;preferably where the barium sulfate is added in an amount of 0.2 to 2% by weight of the total mass of the electrode, and / or where the lignosulfonates are added in an amount of 0.1 to 1.5% by weight of the total mass of the electrode. preferiblemente en donde el sulfato de bario se añade en una cantidad de 0.2 a 2% en peso de la masa total del electrodo, y/o en donde los lignosulfonatos se añaden en una cantidad de 0.1 a 1.5% en peso de la masa total del electrodo.
Independent claims7
563 paragraphs in 61 sections, as filed
(54) Title: MODIFIED SURFACE CARBON HYBRID PARTICLES, METHODS OF REALIZATION AND APPLICATIONS OF THE SAME.
(54) Title: SURFACE-MODIFIED CARBON HYBRID PARTIOLES, METHODS OF MAKING, AND APPLICATIONS OF THE SAME.
(57) Summary
The present disclosure relates to agglomerated surface-modified carbon hybrid particles, the methods for making such surface-modified carbon hybrid particles and their use, for example as conductive additives. Surface modified carbon hybrid particles are characterized by a high surface area and a high content of mesopores. The description also relates to methods for the manufacture of dispersions of such compounds in a liquid medium in the presence of a surfactant and their use as conductive coatings. Also described are polymer compounds charged with the surface modified carbon hybrid particles. The disclosure further relates to the use of surface modified carbon hybrid particles as carbon supports.
(57) Abstract
TIM14415PCT1 ABSTRACTThe present disclosure relates to surface-modified carbon hybrid particles in agglomerated form, methods for making such surface-modified carbon hybrid particles and their use, for example as conductive additives. The surface-modified carbon hybrid particles are characterized by a high surface area and a high mesopore content. The disclosure also pertains to methods for making dispersions of such compounds in a liquid medium in the presence of a surfactant and their use as conductive coatings. Polymer compounds filled with the surface-modified carbon hybrid particles are also disclosed. A further disclosure relates to the use of surface-modified carbon hybrid particles as carbon supports.
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PATENT TITLE No. 360762
Headlines):
IMERYS GRAPHITE & CARBON SWITZERLAND LTD.
Home:
Strada Industríale, CH-6743, Bodio, SWITZERLAND
Denomination:
HYBRID PARTICLES OF MODIFIED SURFACE CARBON, METHODS OF CARRYING OUT AND APPLICATIONS THEREOF.
CIP:
1/42; H01M4 / 583
Classification:
1Λ
1M4 / 625
The patent of refere
Pursuant to the starting date of pres
Inventor (s):
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E. SPAHR
Industrial.
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6WS.412
12108742.0
Validity: VdShjé years
Date of v ^ iidiigientd ^
Date of EA & ádftcióm the Law of n fundaAmtoWilhdj
Who subscribes to this (Official Gazette of the Federation 01/25 / 2006,06 / 05 / 2009,06 / 01/20 and 12th fractions I and III of the Reglam 07/28/2004 and 09/07/2007); Articles 1 'Industrial Property (DOF 12/27/1999, ref ^ M powers in the Deputy General Directors, Departmental Coordinators and other subordinates, 07/29/2004, 08/04/2004 and 09/13/2007).
of Industrial Property 01/26/2004, 06/16/2005, 1 ", 3" fraction V subsection a), 4 "ado on 07/01/2002, 07/15/2004, unique to the Mexican Institute of the 5th paragraph a) of the Agreement that delegates the Regional, Divisional Deputy Directors,. (DOF 12/15/1999. Amended on 02/04/2000,
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HYBRID SURFACE CARBON PARTICLES
MODIFIED, METHODS OF IMPLEMENTATION AND APPLICATIONS
FROM THE SAME
FIELD pg ΙΛ DESCRIPTION
The present disclosure relates to surface modified carbon hybrid particles, methods for the preparation thereof, and their use, for example as conductive additives in a variety of applications.
ANTgCEDgNTgS
Conductive carbon particles are commonly used as fillers to improve conductivity in polymers, ceramics, coatings, electrodes, and in electrochemical systems. For example, carbon conductive additives are used in a variety of primary and secondary batteries such as alkaline zinc / manganese dioxide batteries, zinc carbon batteries, lithium primary and rechargeable batteries, nickel cadmium batteries, batteries of
<td>lead acid</td><td>and batteries</td><td>hydride</td><td colspan="2">metallic</td><td>of</td><td>nickel,</td>
<td>batteries</td><td>lithium-sulfur,</td><td>batteries</td><td>of</td><td>air</td><td>of</td><td>lithium,</td>
<td>batteries</td><td>metal air</td><td colspan="2">with metals</td><td>how</td><td>the</td><td>zinc or</td>
iron, fuel cells, as well as capacitor systems.
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Conductive additives are applied to electrochemical cell electrodes to decrease the electrical resistance of the electrode. Carbonaceous powder materials are often selected as conductive additives due to their light weight and inertia towards acidic and alkaline electrolytes. The conductive additives do not contribute to the electrochemical electrode processes, which means that for a high energy density of the cell, the applied amount of conductive additive is minimized as desired. Typical carbon conductive additives used are conductive carbon black and fine graphite powders (see, eg, ME Spahr, Lithium-ion Batteries-Science and Technology, M. Yoshio, RJ Brodd, A. Kozawa (Eds.), Springer, New York, 2009, chapter 5).
Adding a small amount of conductive carbon to the negative electrode of a lead acid battery leads to an improved charge and life cycle acceptance when the battery operates in the High Charge Partial Speed (HRPSoC) mode such as, for example, it is applied in the use of hybrid electric vehicles (see, for example, K. Nakamura, M. Shiomi, K. Takahashi, M. Tsubota, Journal of Power Sources 59 (1996) 153, M. Shiomi, T Funato, K. Nakamura, K. Takahashi, M. Tsubota, Journal of Power Sources, 64 (1997), 147 and D. Pavlov, P. Nikolov, T. Rogachev Journal of Power Sources
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196 (2011) 5155-5167K). When a pl'Uiuu úuibkL battery is operated at partial charge state (PSoC) the irreversible formation of lead acid sulfate (sulfation effect) causes a significant reduction in the cycle life of the battery (see for example , D. Pavlov, Lead-Acid Batteries-Science and Technology, Elsevier 2011, Chapter 1, pp. 23-26).
In addition to using carbon additives, the use of modified grid designs, fiberglass mats inside the active material, and / or modifying electrolyte compositions are known in the art as other ways to improve acid batteries. conventional lead in start-up, lighting, ignition (SLI) and useful for modes of operation in the lowest charge states (SOC) (cf., for example, D. Pavlov, Lead-Acid Batteries-Science and Technology, Elsevier 2011, Chapter 7). The battery characteristics obtained from these advanced lead acid batteries in shallow high-speed discharge operations make them good candidates for micro-hybrid and hybrid electric vehicles.
The addition of graphite, expanded graphite, activated carbon, carbon black and the negative electrode has been shown to result in improved cycle life of
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lead acid batteries, mainly due to a re-occurrence of the sulfation effect.
Various hypotheses have been proposed to explain the mechanism of the carbon effect on the negative electrode. A study of the influence of a broad spectrum of carbons has been summarized in the literature (PT Moseley, Journal of Power Sources 191 (2010) 134-138 and DP Boden, DV Loosemore, MA Spence, TD Wojcinski, Journal of Power Sources, 195 (2010) 4470-4493). It has recently been shown that carbon must have a high affinity for targeting in order to allow for the formation of a lead carbon skeleton at the negative electrode, while lead plated during electrode formation carried out on the first charge of the freshly assembled fresh cell (D. Pavlov, P. Nikolov, T. Rogachev Journal of Power Sources 196 (2011) 5155-5167). This carbon lead skeleton increases the surface area and, in addition, carbon provides an additional super-condensing effect on the electrode, which provide possible explanations for the acceptance of the increased charge.
In addition to the electrical conductivity properties, conductive additives also have an effect on the electrode structure and porosity. For example, the electrolyte penetration of the electrode can be influenced by the electrode structure and porosity,
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that has an impact on the electrode (see for example
Batteries-Science and Technology, ion resistivity of the
ME Spahr, Lithium-ion
M. Yoshio, RJ Brodd, A.
Kozawa (Eds.), Springer, New York, 2009, Chapter 5.
The positive electrode of a sulfur lithium battery contains sulfur mixed with binder materials and one or more carbon components. Carbon provides electrical conductivity and is further thought to ensure dimensional stability of the electrode during cell discharge when the sulfur content of the positive electrode is reduced by the formation of the discharge products (see, for example, Xiong , Shizhao; Hong, Xiaobin; Xie, Kai; Rong, Lixia, Huagong Jinzhan (2011), 30 (5), 991-996 and Yao, Zhen-Dong; Wei, Wei; Wang,
Jiu-Lin; Yang, Jun; Nuli, Yan-Na, Wuli Huaxue Xuebao (2011), 27 (5) , 1005-1016).
On the other hand, electrochemical cells with air electrodes, contained in cell stacks of
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Fuel or metal air batteries may require carbons in the positive air electrodes. The carbons are believed to act as a support for the metal or metal oxide catalyst and also generate the structure that provides dimensional stability to the electrode. In order to be used on air electrodes, 25 carbon supports are required to demonstrate high resistance to λ
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MEXICAN INSTITUTE
Μ THE PROF1EDAB
INDUSTRIAL
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corrosion to air or oxygen, as it is thought not to do to limit the durability of cells (see, for example, S. Sarangapani, P. Lessner, L. Swette, J. Giner, Proceedings - Electrochemical Society (1992), 92 -ll (Proc. Workshop Struct. Eff. Electrocatal. Oxygen Electrochem., 1992), 510-22, S. Muller, F. Holzer, H. Arai, O. Haas, Journal of New Materials for Electrochemical Systems (1999), 2 (4), 227-232 and F. Maillard, P. Simonov, E. Savinova, Carbon Materials for Catalysis (2009), 429-480).
As mentioned above, natural or synthetic graphite, expanded graphite, activated carbon, and carbon black have been used as conductive additives.
The graphite is made of crystalline carbon. Graphite electronic conductivity is based on the graphite crystal structure consisting of stacked layers of six-membered carbon rings with delocalized electrons in p orbitals conjugated parallel to the graphite layers. The electronic conductivity parallel to the stacked planes is about three orders of magnitude higher than the electronic conductivity perpendicular to the planes. This results in the known anisotropic behavior of electronic conductivity (AW Hull, Phys. Rev. 10 (1917) 661 and W. Primak, LH Fuchs, Phys. Rev. 95 (1) (1954) 22).
The application of graphite, such as conductive additives, could be attributed to properties such as its
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high compaction capacity, resulting in improvements in cell electrode density. It has also been shown that a carbon conductive additive can significantly increase cycle stability and low temperature charge / discharge performance of the electrode. However, although the resistivity at high graphite concentrations is very low, it has been observed that due to the higher percolation threshold for graphite compared to carbon black, relatively large amounts of graphite are required to decrease the electrode resistivity.
Large area graphite is typically obtained by decreasing the particle size of graphite in a grinding process. To prevent oxidation of the graphite product during grinding, grinding can be carried out in an inert gas atmosphere (see, eg, NJ Welham, JS Williams, Carbon 36 (9) (1998) 1309-1315, TS Ong , H. Yang, Carbón, 38 (2000) 2077-2085 and Y. Kuga, M. Shirahige, Y. Ohira, K. Ando, Carbón 40 (2002), 695701). A drawback of conventional grinding processes is that activated carbon and large surface graphite can contain a relatively high amount of trace metals due to the use of metal-based grinding equipment. Metal trace elements can act as electrocatalysts that
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interfere with the desired electrochemical process and cause electrochemical parasitic chemical side reactions that decrease cycle stability and reduce cell life.
Carbon black is an amorphous form of carbon.
The carbon black structure is made up of typically spherical amorphous primary particles that are bonded together by covalent bonds to form larger aggregates. Conductive carbon black typically consists of primary particles 10-50 nm in size and large complex aggregates are often more than 100 nm in diameter. The conductive carbon black aggregates form a conductive network on porous electrodes thus decreasing the electronic resistance (JB Donnet, RP Bansal, MJ Wang, in Carbón. Black Science and Technology, 2nd ed. , Marcel Dekker Inc., New York, 1993). The large volume of intra and inter-aggregate vacuum of conductive carbon black created by the carbon black structure results in high oil absorption numbers. Conductive carbon blacks typically have oil absorption numbers above 150 ml / 100 g (measured in accordance with ASTM D2414-01, see method described below).
Another class of carbonaceous material is activated carbon. Activated carbon is made up of large-area amorphous carbon powders derived from organic products.
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natural as coconut shells or wood products or polymers. These precursors carbonize at temperatures between 700 and 1600 ° C. Subsequent to carbonization, the material undergoes an activation process using steam, CO2, or aqueous zinc chloride solutions at elevated temperatures that increases the BET surface area of the carbonized material. The activation process forms the so-called micro-pores, which are believed to be the cause for the observed increase in surface area (see, for example, H. Marsh, F. Rodríguez-Reinoso, Activated Carbón, Elsevier, 2006).
The use of carbon black as, for example, a conductive additive can be attributed to properties such as high liquid absorption, which appears to lead to superior electrolyte penetration. In addition, the addition of the large-area carbon component has been observed to result in a marked increase in charge acceptance due to the larger electrochemically available inner electrode area, which appears to be a consequence of the larger open structure of the electrode. Another explanation for the positive effect of carbon black additives is that the additional carbon surface charge (supercapacitor effect) can lead to an increase in electrochemical capacity, which is a desired property, for example, driving
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negative acid battery electrodes and supercapacitors.
However, despite requests for large-area carbons as carbon additives, some adverse consequences have been observed with respect to life cycle, high speed performance and low temperature discharge. An additional problem associated with large surface carbon components is high water absorption as a paste formulation, which can interfere with the production of electrodes containing such additives.
Furthermore, the decomposition of the aqueous electrolyte, which occurs as a parasitic side reaction in the lead acid battery during charging, leads to the formation of hydrogen on the negative electrode. The decomposition rate of the electrolyte has been found to be accelerated by the large surface area of carbon and in the presence of typical metal impurities. Furthermore, the oxygen formed in this reaction at the positive electrode could be a cause of oxidative carbon corrosion that seems to occur particularly with large surface amorphous carbons.
It can be seen from the properties mentioned above that conductive carbon additives appear to have a significant impact on the
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electrode engineering, its properties, and the electrode manufacturing process ..
As described above, conductive carbon black and graphite appear to have many complementary properties when considered as conductive additives in electrodes. As both low and large surface carbons (graphite and amorphous carbon powders) have been shown to exert positive effects they still suffer from different drawbacks in desired applications, attempts to use a mixture of the two have been described in the literature (see, for example, M. Fernandez, Batteries & Energy Storage (BEST) Spring 2011 81-93 and M. Fernandez, N, Muñoz, R. Nuno, F. Trinidad, Proceedings of the 8<sup>th</sup> International Conference on Lead Acid Batteries, Extended Abstract # 6, Lead Acid Battery Department of the Bulgarian Academy of Science, Sofia, Bulgaria, June 7<sup>th</sup>-10<sup>th</sup>, 2011, p. 23-28). However, such blends are fraught with problems. For example, in the negative electrode manufacturing process, the required homogeneous mixing of two carbon components, one of which has a very low bulk density in the lead oxide paste formulation, can be problematic.
Accordingly, it is an object of the invention to provide an alternative carbon material that can be made reliably, easy to handle and has a
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excellent physicochemical and electrochemical properties, especially when used as a conductive additive, as well as methods for its preparation.
SHORT DESCRIPTION
The inventors have found that surface modified carbon hybrid particles comprising an amorphous carbon coated graphite core show excellent properties, for example, exhibiting a large surface area combined with a high content of mesopores, which appears to provide favorable mechanical and electrochemical properties. For example when used as a carbon additive.
Thus, according to a first aspect, the present invention is directed to agglomerate-modified surface-modified carbon hybrid particles with a large BET surface. and a large area of mesopores, as measured by functional density theory (DFT), based on the parameters below.
Certain embodiments of the agglomerate-modified surface carbon hybrid particles of the present invention are preferably characterized as having a BET surface of at least 50 m<sup>2</sup>/ g and not more than 800 m<sup>2</sup>/ g, a DFT mesopore area of at least 40 m<sup>2</sup>/ gy
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not greater than 400 m<sup>2</sup>/ g, where the DFT mesopore area is equal to or less than the BET surface.
According to a second aspect, the present invention is directed to a method for the manufacture of surface modified carbon hybrid particles, wherein the method comprises grinding a graphite in a gas-tight sealed mill and carbon functionalization hybrid resulting from controlled oxidation. In some embodiments, the method further includes maintaining the product of the grinding step in the mill to allow the agglomeration of the ground primary particles to be terminated prior to functionalization. Optionally, the method may also include preparing the deagglomerated product, dispersing the agglomerated product from the functionalization step in a liquid in the presence of a stabilizing amount of a surfactant or in a polymer by the main application of shear forces.
Accordingly, the dispersion-modified surface carbon hybrid particle dispersions obtainable by the above method are a further related aspect of this invention. Another aspect of the invention is the use of a dispersion of the surface modified carbon hybrid particles as a conductive or lubricating coating.
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However, another aspect of the present invention relates to a polymer compound filled with the surface modified carbon particles of the invention and a battery electrode comprising the surface modified carbon particles of the invention as a conductive additive, and, optionally, other compounds such as barium sulfate and / or lignosulfonates as functional additives.
A further aspect of the present invention is directed to the provision of a carbon conductive additive comprising the agglomerated hybrid surface modified particles, where the conductive additives can be used in a variety of applications such as in lead acid batteries , lithium sulfur batteries, double-layer electrochemical capacitors, and others.
Finally, a further aspect of the invention relates to the use of surface modified carbon hybrid particles as catalyst supports.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows the carbon D hybrid Raman spectra compared to synthetic graphite, expanded graphite, and carbon black. Compared to graphite and expanded graphite, band D increased against
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INSTITUTO MEXICANO M the ηοηεοΑ »INDUSTRIAL increased G band of the carbon D hybrid indicates an increased amorphous character in the surface regions, while compared to carbon black, the D carbon hybrid exhibits a higher intensity of the G band indicating a higher degree of graphitization.
Figure 2 is a C-carbon hybrid scanning electron microscope image illustrating the morphology of amorphous carbon on the surface of secondary particles (particle microstructure).
The is a C-carbon hybrid transmission electron microscope image showing the morphology of a primary particle consisting of a graphite skeleton and mesoporous amorphous carbon on top of the graphite skeleton.
Figure 4 shows the total surface area of surface, surface area of micropores and surface area of mesopores of the hybrid modified surface carbon particles of Example 1 compared to carbon black, expanded graphite and activated carbon.
Figure 5 shows the pore volume, micropore volume, and total mesopore volume of the surface-modified carbon hybrid particles of Example 1 compared to carbon black, expanded graphite, and activated carbon.
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Figure 6 shows the particle size and geometric surface change of Sample D of the surface-modified carbon hybrid particles of Example 1 during deagglomeration.
Fig. 7 shows the pressing pressure density of the corresponding carbon A hybrid and carbon D hybrid compared to expanded graphite, carbon black, synthetic graphite, and activated carbon. Carbon hybrids indicate an increase in density compared to pressed carbon and activated carbon black, although it is still slightly lower than that of graphite and expanded graphite.
Figure ^ 8 illustrates the mechanical work (compaction energy) required to achieve the corresponding pressing density of carbon A hybrid and carbon D hybrid compared to expanded graphite, carbon black, synthetic graphite, and activated carbon.
The Figuya 9 shows the electrical resistivity, in the corresponding sample densities, carbon A hybrid and carbon D hybrid compared to expanded graphite, synthetic graphite and carbon black. The high conductivity of carbon hybrids is indicated, as well as their hybrid character between graphite and carbon black.
IMPI
<img file="MX360762B_D0024.tif" />
<td>The figure</td><td>10 shows a microscopy image</td>
<td>electronics</td><td>sweep illustrating the lining</td>
<td>homogeneous of the</td><td>lead crystals on an electrode that</td>
contains carbon D hybrid or carbon E hybrid.
DETAILED DESCRIPTION OF EXEMPLARY MODALITIES OF THE INVENTION
The inventors have found that hybrid carbon particles comprising a graphite core coated with an amorphous carbon and having a modified surface, large surface area and high content of mesopores, exhibit excellent mechanical and electrochemical properties. These favorable properties make them a good material to be used among other things as conductive additives, as conductive coatings and as carbon supports in a variety of applications.
Surface Modified Carbon Hybrid Particles
The surface modified carbon hybrid particles of the present invention comprise a graphite core which is coated with amorphous carbon, which in agglomerated form is characterized inter alia by a high BET surface area of at least 50 m<sup>2</sup>/ g, or at least 80 m<sup>2</sup>/ g, or at least 100 m<sup>2</sup>/ g, as long as it does not exceed 800 m<sup>2</sup>/ g, or 700 m<sup>2</sup>/ g, or 600 m<sup>2</sup>/ g, or 500 m<sup>2</sup>/ g. The
<img file="MX360762B_D0025.tif" />
particles are further characterized by a DFT mesopore zone of at least 40 m<sup>2</sup>/ g, or at least 60 m<sup>2</sup>/ g, or at least 70 m<sup>2</sup>/ g, or at least 80 m<sup>2</sup>/ g, as long as it does not exceed 400 m<sup>2</sup>/ g, or 300 m<sup>2</sup>/ g, or 200 m<sup>2</sup>/ g.
In many embodiments, a characteristic of large surface modified surface carbon hybrid particles is that the ratio of mesopores as opposed to surface micropores is high, where the ratio of the DFT mesopore area to the total of pore area is DFT 20 to 90%, or 40 to 90%, or 45-75%, or 50 to 70%. Similarly, the DFT mesopore volume of surface-modified carbon hybrid particles is at least 0.10 cm<sup>3</sup>/ g, or at least 0.15 cm<sup>3</sup>/ g, or at least 0.17 cm <sup>3</sup>/ g, or at least 0.29 cm<sup>3</sup>/ g, and / or the ratio of DFT mesopore volume to total DFT pore volume is 50 to 95%, or 70 to 95%, or 80 to 95%. These data demonstrate that a large proportion of the surface pore surface is made up of mesopores and an even larger proportion of the total pore volume is made up of mesopores.
Typically, the hybrid carbon particles are present in the form of an agglomerate, which results in the formation of a microstructure where the non-agglomerated sub-micron particles are bonded together to form the agglomerates of microstructures. It has been found that
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<img file="MX360762B_D0026.tif" />
These microstructures act as hosts with good mechanical stability for use on sulfur cathodes in lithium sulfur batteries. In certain embodiments of the present invention, the agglomerates are characterized (by the wet dispersion method described below) as having a Dg value<sub>0</sub> between 20 and 60 μιη, or from 30 to 50 μιη, or from 40 to 50 pm and / or a D <sub>50</sub> value from 7 to 15 pm, or from 7 to 12 pm and / or a Dio value of 0.3-4 pm, or 0.43 pm, or 0.5 to 2 pm. In some modalities, the agglomerates can also be characterized by having a Dg value<sub>0</sub> from 50 to 300 pm, or from 100 to 300 pm, or from 100 to 200 pm, or 150-200 pm when using the dry dispersion method described below. The differences in the Dgo value depending on whether the dry or wet dispersion method is used for PSD laser diffraction measurement can be explained by the shear forces plus
<td colspan="2">discharges applied to</td><td>chipboards</td><td>in</td><td>the</td><td>method</td><td>of</td>
<td>dispersion</td><td>wet,</td><td>what seems</td><td colspan="4">break the majors</td>
<td>particles</td><td>chipboard</td><td>during the</td><td>stage</td><td>of</td><td>dispers</td><td>ion</td>
<td>required</td><td colspan="2">for measurement while</td><td>than</td><td>the</td><td>method</td><td>of</td>
Dry dispersion appears to have less impact on the agglomerated carbon hybrid particle size. In any case, the modified hybrid particles mentioned in the less surface carbon agglomerated product present refer to the one specified
<img file="MX360762B_D0027.tif" />
contrary. Similarly, unless otherwise specified, the values given herein (for example, BET SSA, mesopore area or volume, etc.) also refer to agglomerated products and not primary particles (a often sub-microns).
It has been found that the hybrid nature of hybrid carbon particles seems to combine the properties of both conductive graphite and carbon black of the large surface. For example, when hybrid particles have been used as conductive carbon additives in battery electrodes, good electrical conductivity as well as excellent compressibility have been observed, even at lower concentrations compared to graphite. As mentioned above, the use of graphite and carbon black mixtures has been attempted in the prior art, but these suffer from the disadvantage that the mixture is generally difficult to handle in the manufacturing process. Hybrid carbon particles as described herein (which are typically present in agglomerate form) are in contrast therewith to produce and handle
<td>easily,</td><td>While</td><td>than</td><td>still</td><td>I know</td><td>they benefit from</td><td>the</td>
<td>properties</td><td>favorable</td><td>of the</td><td>graphite and</td><td colspan="2">carbon black.</td><td></td>
<td colspan="2">In accordance with</td><td>a</td><td>modality</td><td>of</td><td>the invention,</td><td>the</td>
surface modified carbon hybrid particles
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<img file="MX360762B_D0028.tif" />
they are also characterized by an increase in the concentration of quimisorbide oxygen groups on the carbon surface, which is herein referred to as surface oxides. Therefore, in some embodiments of the invention, the oxygen content of the surface modified carbon hybrid particles, measured according to the method below, is at least 0.45% w / w, or at least 0.85% w / w p, or at least 1% w / w, or at least 2% w / w, or at least 3% w / w and typically not more than 7% w / w, or not more than 8% w / w. As can be seen in Table 2 below, comparative examples of a variety of known carbon materials have an oxygen content of 0.41% w / w or below. Since some of the oxygen groups on the surface of the particles are effectively carboxyl groups, it is not surprising that in most embodiments, surface modified carbon hybrid particles have an acidic pH, i.e. a pH below 7.0, preferably below 6.7, or below 6.5, or below 6.0, or below 5.5, or even below 5.0.
Without wishing to be bound by theory, the concentration of surface oxides appears to be especially relevant to the affinity of lead particles. This is particularly important when using the hybrid of surface carbon particles.
<img file="MX360762B_D0029.tif" />
IMPI
MEXICAN KSTITUTO
OI m MONEDAD
INDUSTRIAL
<img file="MX360762B_D0030.tif" />
modified as conductive additives in the negative electrode of a lead acid battery. Furthermore, the combination of high content of mesopores and high concentration of surface oxides seems to lead to excellent lead coating properties (cf. Figure 10).
The deposition density of surface modified carbon hybrid particles according to some modalities will typically be 0.35-0.7 g / cm<sup>3</sup>, or from 0.4 to 0.7 g / cm <sup>3</sup>. Alternatively, surface modified carbon hybrid particles can also be characterized by their so-called Scott density. Therefore, in many modalities the Scott density of the surface-modified carbon particle typically ranges from 0.2 to 0.6 g / cm.<sup>3</sup>, or 0.25 to 0.6 g / cm<sup>3</sup>.
Interestingly, due to the particular morphology of surface-modified carbon hybrid particles, oil absorption is significantly less than other carbons with comparable pore volume BET and SSA, eg carbon black or activated carbon. In some embodiments, the oil absorption is 150% w / w or less, or 140% w / w or less, or 120% w / w or less, 100% w / w or less, or 80% w / w or less. The method used to determine the oil absorption of the hybrid carbon particles is the same method used
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<img file="MX360762B_D0031.tif" />
to determine the oil absorption for graphite, described below. The oil absorption observed for hybrid carbon particles is in the range of the typical oil absorption values obtained for graphite and is therefore significantly less than for carbon black or activated carbon.
For some embodiments, surface modified carbon hybrid particles may be further characterized by an ash content of less than 0.1%, or below 0.08%, or below 0.05%, and / or a Fe content value of below 500 ppm, or below 400 ppm, or below 300 ppm, or below 200 ppm, or below 160 ppm. In some embodiments, particularly when nonmetallic grinding media are used in the grinding step, for example, grinding media made of ZrÜ2, AI2O3 or ceramic materials, the surface modified carbon hybrid particles can be characterized by a value of Fe content of below 50 ppm, or below 10 ppm, or below 5 ppm.
Relative to the crystal structure, surface modified carbon hybrid particles in certain embodiments have a crystallite size L<sub>to </sub>(measured by Raman spectroscopy) from 1 to 10 nm, or from 3 to 8 nm, or from 4 to 6 nm, and / or a crystallite size L<sub>c</sub> (such
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<img file="MX360762B_D0032.tif" />
as measured by XRD) from 10 to 100 nm, or from 10 to 60 nm, or from 10 to 50 nm.
In most modalities, the c / 2 value of surface modified carbon hybrid particles is between 0.3355 to 0.3400 nm, and preferably between 0.3358 to 0.3380 nm. Accordingly, the degree of graphitization of the surface modified carbon hybrid particles (which is calculated according to the method described below with the aid of the c2 value) typically varies from 80 to 95%, or from 85 to 95%, or 90 to 95%.
In additional embodiments, surface modified carbon hybrid particles, when present in the form of a deagglomerate (eg, in a dispersion stabilized with a wetting agent), can be characterized by a particle size distribution with the following values:
a value D<sub>90</sub> of non-agglomerated particles less than 10 pm, or less than 8 pm, or less than 5 pm, or less than 4 pm, or less than 3 pm, or less than 2 pm, or less than 1.8 pm; and / or a D value<sub>50</sub> of non-agglomerated particles less than 4 pm, or less than 2 pm, or less than 1 pm, or less than 0.75 pm, or less than 0.4 pm, or less than 0.3 pm; and / or a Di value<sub>0</sub> of non-agglomerated particles less than 0.6 pm, or less than 0.4 pm, or less than 0.2 pm, or less than 0.15 pm.
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<img file="MX360762B_D0033.tif" />
Compaction densities at corresponding pressures have been found to be higher for surface-modified hybrid carbon particles than for carbon black and other amorphous carbons such as activated carbon. For example, as can be seen in Figure 7, hybrids of surface-modified carbon and amorphous carbons at a pressure of 4 kN / cm<sup>2</sup> they have a density of about 1-1 0.75 g / cm<sup>3</sup> and 0.5-0.75 g / cm<sup>3</sup>, respectively and / or at a pressure of 8 kN / cm<sup>2</sup> they have a density of about 1.2-1 0.9 g / cm<sup>3</sup> and 0-7-0.9 g / cm<sup>3</sup>, respectively, and / or at a pressure of 12 kN / cm<sup>2</sup> it has a density of about 1.3-1 0.9 g / cm<sup>3</sup> and 0.75-1.0 g / cm<sup>3</sup>, respectively, and / or at a pressure of 20 kN / cm<sup>2</sup> have a density of 0.5 to 2.25 1 g / cm<sup>3</sup> and 0.8-1.2 g / cm<sup>3</sup>, respectively.
Furthermore, the compaction energy to achieve a given compaction density is lower for surface modified carbon hybrid particles than for amorphous black carbon and others such as activated carbon, which can be seen in Figure 8. For example , in a mechanical work of 100 kg * cm the density of the composite materials of the surface modified carbon hybrid particles is between about 1 0.2-2 g / cm<sup>3</sup>, while for amorphous carbons the density reached is between about 0.55 to 0.65 g / cm<sup>3</sup>. Of the
IMPI
<img file="MX360762B_D0034.tif" />
similarly, in a mechanical work of 2UU kg<sup>+</sup>cm the densities of surface-modified carbon hybrid particulate materials and amorphous carbons is around 2 to 2.75 g / cm<sup>3</sup> and 0.70-0.75 g / cm<sup>3</sup>, respectively. Also in some modalities, the percentage of elastic recovery observed is lower for surface modified carbon hybrid particles at 14-19% than for carbon black, which has a value of about 88%.
It has been postulated that the lower electrical resistivities that have been obtained from surface modified hybrid carbon particles compared to carbon black could be due to good compressibility at high compaction densities which are supposed to lead to better electrical inter-contacts. granules of surface modified carbon hybrid particles. In fact, at corresponding compaction densities, the electrical resistivity that can be obtained for the surface-modified hybrid carbon particles approximates that of graphite, which in turn is less than the resistivity obtained with carbon black.
Methods for Preparing Modified Surface Hybrid Carbon Particles
<img file="MX360762B_D0035.tif" />
. In another aspect, the present invention provides a method of manufacturing hybrid carbon particles of
<td colspan="2">modified surface as</td><td>define</td><td colspan="2">in the present, that</td>
<td>understands</td><td>the following steps:</td><td></td><td></td><td></td>
<td>to)</td><td>graphite grinding</td><td>in a</td><td>mill of</td><td>sealed</td>
<td>airtight</td><td>algae; and</td><td></td><td></td><td></td>
<td>b)</td><td>functionalization of</td><td>the</td><td>particles</td><td>hybrid</td>
resulting from carbon by controlled oxidation.
As used herein, controlled oxidation is a planned and deliberate step under controlled conditions that results in surface oxidation of the hybrid carbon particles obtained from the grinding step. This is demonstrated, for example, in Table 8, where it is shown that before functionalization the oxygen content was approximately 0.21% w / w, whereas after functionalization (intensive mixing of hybrid carbon particles in the air without external heating) the oxygen content was approximately 3.4% w / w.
In some modalities of this aspect, the grinding stage is carried out until the value D<sub>90</sub> of non-agglomerated particles, as determined by the wet dispersion method, is less than 5 pm, or less than 3 μιη, or less than 2 pm, or less than 1 pm 0.8 and / or until the value D<sub>5</sub>q of non-agglomerated particles is less than 2 pin, or
<img file="MX360762B_D0036.tif" />
IMPI ® <ST! TUTO MfcXfCANC DC INDUSTRIAL PROPERTY
<img file="MX360762B_D0037.tif" />
less than 1 μπι, or less than 0.75 pm, or less than 0.4 pm, or less than 0.3 pm and / or until the Dio value of non-agglomerated particles is less than 0.6 pm, or less than 0.4 pm, or less than 0.2 pm, or less than 0.15 pm.
In certain modalities, the product of the grinding process (step a) is kept in the gas-tight sealed mill for at least 15 minutes, or at least 30 minutes, or at least 45 minutes before carrying out the functionalization (the stage b). This maintenance step allows the agglomeration of the primary (sub) miera particles to be completed. In some embodiments, this maintenance step in the gas-tight sealing mill is carried out until the agglomerated carbon hybrid particles (determined using the wet dispersion method described below) have the following size distribution values particle:
<td>a value D<sub>90</sub> between 20 and 60 pm,</td><td>or from 3 0 to</td><td>50 pm, or</td>
<td>from 40 to 50 pm, and / or</td><td></td><td></td>
<td>a value D<sub>50</sub> from 7 to 15 pm, or</td><td>7 to 12 pm,</td><td>me</td>
<td>a value Di<sub>0</sub> from 0.3-4 pm, or 0.4-3</td><td>pm, or 0.</td><td>5 to 2 pm.</td>
Alternatively, the maintenance stage in these modalities is carried out until the value D<sub>90</sub> of the agglomerated carbon hybrid particles, as determined by the dry dispersion method described in
<img file="MX360762B_D0038.tif" />
then ranges from 50 to 300 pm, or ~ dg ΊΌ0 a '<sup>,,</sup>'3'frQ · pm, —cr from 100 to 200 pm, or 150-200 pm.
The subsequent functionalization process was found to create the desired surface oxide chemistry and, in addition, appear to saturate the surface of activated carbon.
In one embodiment of the invention, controlled oxidation is carried out by stirring the material in a mixer. The mixer can be an intensive batch mixer, which serves to mix the material quickly, homogeneously and reproducibly. The mixer could also be a paddle batch mixer or a two-axis paddle batch mixer, for example, which allows for a greater degree of fluidization of the solid particles facilitating the contact of each carbon hybrid particle with the gas reaction.
In many embodiments of the invention, controlled oxidation is carried out or at least initiated at a temperature of not more than 400 ° C, or not more than 300 ° C, or not more than 200 ° C, or not more than 100 ° C, or not greater than 50 ° C, or not greater than 30 ° C. Therefore, there will be no burning of the carbonaceous material as observed in surface modification processes at temperatures above 400500 ° C. However, as mentioned briefly before, due to the exothermic reaction of the gas it contains
<img file="MX360762B_D0039.tif" />
oxygen with the carbon particles, a temperature rise is often observed (eg at about 150 ° C) in the mix even if there is no external heating applied to the mix.
In some embodiments, controlled oxidation is carried out until the oxygen content is at least 0.45% w / w, or at least 0.85% w / w, or at least 1% w / w, or at least 2% w / w, or at least 3% w / w. Likewise, controlled oxidation is in most modalities carried out until the pH is below 7.0. In some embodiments, the pH of the particles will be below 6.7, below 6.5, below 6.0, below 5.5, or even below 5.0.
Controlled oxidation is typically carried out in the presence of air, moisture, oxygen, another oxidizing gas, and / or an oxidizing liquid. Oxidizing gas may be NO<sub>X</sub>, ozone or carbon dioxide and the oxidizing liquid can be hydrogen peroxide or nitric acid. In the case of a liquid functionalization process, the resulting product is filtered off and dried after functionalization. A typical functionalization is performed in a mixer that is fluidized with air for at least 15 minutes, or at least 20 minutes, or at least 30 minutes, or at least 45 minutes, or at least 1 hour.
<img file="MX360762B_D0040.tif" />
Examples of suitable types of equipment for the grinding step (step (a)) described herein include, but are not limited to, vibration mills, rocker mills, swing mills, planetary ball mills, drum mills or tumbling, ball mills, crushing or crushing mills (horizontal and vertical), pearl mills, and others. In some embodiments of the invention, the sealing mill used is a crushing mill or a ball mill, such as a rotary mill, a tumbling mill, or preferably a vibration mill. Grinding media can vary in shape (eg spheres, cylinders, cylpeps, rods, etc.), size, and material (eg steel, iron, ceramic, ZrO<sub>2</sub>, A1<sub>2</sub>OR<sub>3</sub>, etc.) according to the configuration of the individual plant or the machine used.
In vibration mills, impact forces are generated by the collision of the balls when the drum container is vibrated. Vibration mills are known to work efficiently as impact forces can be generated efficiently in degrees of fill, even above 90%. This is an average method compared to grinding in a rotating ball mill, for example, which generally applies higher impact and higher shear forces on the material to
<img file="MX360762B_D0041.tif" />
grind (depending on the speed of rotation and the degree of filling). Consequently, in a vibration mill the desired product is formed faster while the external particle contamination remains lower due to less abrasion of the balls and the interior walls of the grinding compartment. Contamination with metallic impurities is therefore kept low, but can of course be totally excluded through the use of non-metal based balls and coatings.
Therefore, the grinding media used in the mill can, according to an embodiment of the invention, be made of non-metallic materials such as ZrO2, AI2O3 or ceramic. Optionally, the mill is equipped with an internal non-metallic coating, preventing further metal contamination from the particles.
Furthermore, in many embodiments of this aspect of the invention, grinding (step a)) is carried out for a period of not more than 150 hours, or not more than 96 hours, or not more than 84 hours, or not more than 72 hours or not more than 60 hours. A typical grinding process involves mechanical treatment of natural or synthetic graphite, ideally with high purity in sealed gas-tight ball mills or preferably vibration mills. It has been found that the total ash content can
<img file="MX360762B_D0042.tif" />
be further minimized if high purity graphite is used as a starting material. The process does not depend on the particle size of graphite but in practice, thick graphite is often used as a starting material.
In certain modalities, the degree of filling of the ball mill must be less than 75%, or below 80% and the speed of rotation of the mill must be high enough so that the balls are transported to the top of the cylinder drum and fall into the graphite / ball mass at the bottom of the drum to maximize impact forces vs. shear forces on treated particles.
Carbon hybrid materials can also be produced by a dry grinding process, from suitable carbon materials, for example as described in Example 1 and 3 below, by any type of mill vibration or rotation. dry with a gas-tight grinding chamber filled with grinding media.
In general, the person skilled in the art will be aware that the main grinding parameters will have to be readjusted in order to reach the target large area (and product specifications) within industrially acceptable time limits, that is, in order to reduce grinding time, size of
<img file="MX360762B_D0043.tif" />
IMPI or A MEXICAN INSTITUTE • J * »t LA MONEDAD
INDUSTRIAL graphite batch, type of grinding medium, the rigged and “the shape, the mill filling factor and the weight ratio (graphite to grinding media) will have to be optimized for each specific type of equipment selected.
Polymers Compounds Filled with Modified Surface Carbon Hybrid Particles
The polymer compounds charged with the surface modified carbon particles described herein are another aspect of the present invention, exhibiting excellent electrical and thermal conductivity, along with good mechanical properties. Examples of polymers can be, but are not limited to, polypropylene, polyethylene, polystyrene, polyamide, polyimide, polyphenylene sulfide, and elastomers such as synthetic or natural rubber. It has been observed that surface modified carbon hybrid particles can in most cases be used directly, i.e. as agglomerates, to prepare the filled polymer compound as it has been observed that typical extrusion processes apply sufficient shear stress to disperse the agglomerates into the primary (or at least finer) particles which are then stabilized in the polymer.
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<img file="MX360762B_D0044.tif" />
Use of Modified Surface Hybrid Carbon Particles as Additives in Battery Electrodes
Because the surface modified carbon hybrid particles as described herein have excellent electrochemical properties, a battery electrode comprising the surface modified carbon particles as a conductive additive represents a further aspect of the invention. Due to the particle size below the primary particle size, the present carbon particles exhibit favorable properties, particularly in electrodes containing sub-micron size electrode materials.
In some embodiments, the battery electrode material may additionally include barium sulfate, which is known to prevent deposition of lead sulfate as a thin passivation film on the surface of the electrode material by acting as a site (chemically inert) for precipitation of lead sulfate. Barium sulfate is generally used at an average particle size of about 1 um although it can also work with particle sizes slightly larger than 1 pm.
In such embodiments, barium sulfate is added in an amount of about 0.2 to about 2%, preferably 0.5 to 1.5% or 0.7 to 1.3%, and more
<img file="MX360762B_D0045.tif" />
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL NtONEDAD
<img file="MX360762B_D0046.tif" />
preferably at about 1% by weight of the total mass of the electrode (see, eg, Boden, Power Supplies J. 73 (1998), pp. 89-92).
In addition, or alternatively, such battery electrodes may contain, in addition to the surface-modified carbon hybrid particles and possibly barium sulfate, also lignosulfonates as an additional additive. Lignosulfonates are complex aromatic polyethers and are known to prevent flocculation of lead particles due to their amphiphilic nature where the large hydrophobic organic moiety adsorbs on the surface of the lead particles, while the hydrophilic inorganic component is in contact with the aqueous electrolyte phase, thereby preventing coalescing particles or even sintering (see, for example, again Boden, Power sources J. 73 (1998), pp. 89-92).
In such embodiments, the lignosulfonates are typically added in an amount of from about 0.1 to 20 about 1.5%, preferably 0.3 to 1 0.0%, and most preferably to about 0.75% by weight of the total mass of the electrode.
Carbon, barium sulfate, and lignosulfonates are commonly used as additives and collectively referred to as expanders. Therefore, an additional modality of wr *
<img file="MX360762B_D0047.tif" />
The invention relates to mixtures of the surface-modified carbon hybrid particles with lignosulfonates and / or barium sulfate. Such mixtures can for example be used as an additive for the negative electrode of lead acid batteries.
The use of battery electrodes containing the surface-modified hybrid carbon particles, and optionally barium sulfate and / or lignosulfonates, in lead acid batteries is yet another aspect of the invention. The modified surface carbon hybrid particles described herein are suitable for lead coating, which is believed to be due to the high content of mesopores and the chemistry of the surface oxide group of hybrid surface carbon particles. modified. Furthermore, compared to other carbon atoms having a similar surface area, better resistance against oxidative corrosion and electrolyte decomposition has also been observed in lead acid batteries for the 20 hybrid carbon particles described herein.
Furthermore, increasing the concentration of surface oxide surface groups causes a more polar carbon surface and therefore increases the hydrophilicity of the carbons. This enhancement of the wetting of the carbon hybrid surface in between
<img file="MX360762B_D0048.tif" />
IMPI aqueous industrial leads to advantages in the manufacturing process of negative electrode mass such as carbon hybrid, compared to graphite or typical carbon black, more easily mixes in aqueous lead oxide paste and other electrode components negatives.
In a further embodiment of this aspect, the battery electrodes containing the surface modified carbon hybrid particles can be used as positive electrodes of the sulfur lithium batteries. Due to the microstructure of the surface modified carbon hybrid particles, they can act as a host for sulfur acting as an electrochemically active component in the positive electrode. Positive electrodes containing absorbed sulfur within the microstructure of surface modified carbon hybrid particles have been found to exhibit excellent mechanical stability and resistance against oxidative corrosion.
In another embodiment of the invention, the battery electrode described herein can be used as an electrochemical double layer capacitor. In some embodiments, double-layer electrochemical capacitors have an average capacitance above 7F / g, or above 6 F / g, or above 5.5 F / g.
<img file="MX360762B_D0049.tif" />
IMPI
Use of Modified Surface Hybrid Carbon Particles as Catalyst Supports
The use of the surface modified carbon particles defined herein according to the carbon supports represent another aspect of the invention. When used as a carbon backing, or skeleton, for example, on air electrodes used in fuel cells and metal air electrodes, metal or metal oxide catalysts can be finely dispersed on the amorphous carbon surface . The surface oxides and pores are believed to function as anchor points to stabilize the finely dispersed catalyst on the carbon surface, which appears to suppress any segregation effects during preparation and operation. High and homogeneous dispersion of the metal catalyst cannot be achieved in typical graphite powders, which are believed to be at least in part due to the absence of the aforementioned surface morphology shown by the hybrid carbon particles as describes in the present.
Dispersions of Hybrid Carbon Particles d
Modified Surface
A dispersion of the surface modified carbon particles described herein in a liquid
<img file="MX360762B_D0050.tif" />
in the presence of a surfactant to form colloidal carbon dispersions represents another aspect of the present invention. These dispersions can be obtained by a process involving the cleavage of the agglomerate particles obtained from the functionalization step by applying energy mainly in the form of shear forces and the stabilization of the primary particles by the use of surfactants (for example, wetting agents) in liquid polar media.
This dispersion process therefore represents a further embodiment of this aspect of the invention. This dispersion process can, for example, be carried out in an attrition mill. It appears that the morphology of the polar surface of the hybrid carbon particles facilitates the wetting process with water or polar solvents, which aids in the preparation of colloidal carbon dispersions. Accordingly, another related aspect relates to the use of the surface modified carbon particles described herein to form a dispersion in a liquid in the presence of a surfactant by applying shear force to deagglomerate the particles. Examples of surfactants that can be used are, but are not limited to n-alkyl oxide,
IMPI
<img file="MX360762B_D0051.tif" />
polyethylene, polyethylene glycol, polyethylene iso-alkyl oxide or polyethylene glycol.
The dispersions described above can for example be used as a base for conductive coatings.
Measurement Methods
Percentage (%) values specified herein are by weight, unless otherwise specified.
Bet Surface Area Specify Volume And DFT Area Micropore And Mesopore
The method is based on the recording of the liquid nitrogen absorption isotherm in the range of p / pO = 0.04 to 0.26, at 77 K. The adsorption of nitrogen gas is carried out on a Quantachrome Autosorb-1. Following the procedure proposed by Brunauer, Emmet and Teller (Gas adsorption in multimolecular Layers, J. Am. Chem. Soc, 1938, 60, 309319), the monolayer capacity can be determined. Based on the cross sectional area of the nitrogen molecule, the monolayer capacity and the weight of the sample, the specific surface can be calculated. The measurement isotherm in the pressure range p / pO 0.01 -1, at 77K are measured and processed with the DFT calculation in order to
IMPI
<img file="MX360762B_D0052.tif" />
evaluate the distribution of pore size, micro and meso pore volume and area. Reference: Ravikovitch, P., Vishnyakov, A., Russo, A., Neimark, A., Langmuir 16 (2000) 2311-2320; Jagiello, J., Thommes, M., Carbon 42 (2004) 1227-1232.
Particle Size Distribution (PSD)
The presence of particles within a coherent light beam causes diffraction. The dimensions of the diffraction pattern are correlated with the particle size. A parallel beam from a low power laser illuminates a cell that contains the sample suspended in water. The beam leaving the cell is focused by an optical system. Next, the distribution of light energy in the focal plane of the system is analyzed. The electrical signals provided by the optical detectors are transformed into the particle size distribution by means of a calculator. The method provides the ratio of the total volume of particles to a discrete number of size classes that form a volumetric particle size distribution (PSD). The particle size distribution is typically defined by the Dio, D values.<sub>50</sub> and Dgo, where 10 percent (by volume) of the particle population is below the Dio value, 50
IMPI
<img file="MX360762B_D0053.tif" />
percent (by volume) of the particle population is below the D value<sub>50</sub> and 90 percent (by volume) of the particle population is below the D value<sub>90</sub>.
The laser diffraction particle size distribution data cited herein has been measured with a Malvern Mastersizer S apparatus. For PSD determination, a small sample of a carbon material is mixed with a few drops of agent and a small amount of moisturizing water. The sample prepared in the described manner is introduced into the
<td colspan="2">storage</td><td colspan="3">of the apparatus (Malvern</td><td>Mastersizer S)</td><td>and</td>
<td>after</td><td> 5</td><td>minutes</td><td>of</td><td>treatment</td><td>ultrasonic to</td><td>a</td>
<td>intensity</td><td>of the</td><td>100% and</td><td>the</td><td colspan="3">pump and stirrer speed</td>
<td>adjusted to</td><td> 40%,</td><td>Is taken</td><td>a</td><td>measurement.</td><td></td><td></td>
<td>How</td><td>a</td><td colspan="3">alternative to method</td><td>dispersion</td><td>in</td>
<td>wet from</td><td>the</td><td colspan="2">particles</td><td>described</td><td>previously,</td><td>a</td>
Malvern dry dispersion measure can also be applied, so dust samples are dispersed by means of an air jet (MALVERN DRY POWDER FEEDER MSX64). The observed PSD values, in particular D values<sub>90</sub>, by the dry dispersion method they were found to be considerably higher for the agglomerates described herein since the shear forces applied during wet dispersion were
<img file="MX360762B_D0054.tif" />
<img file="MX360762B_D0055.tif" />
IMPI
THE MEXICAN INSTITUTE OF NORTH INBUJTMAL have found that they are sufficient to break the
<td>chipboards</td><td>in</td><td>particles</td><td>plus</td><td>small in comparison</td><td>with</td>
<td>the method</td><td>of</td><td>dispersion</td><td>in</td><td>dry where the forces</td><td>of</td>
<td colspan="2">shearing</td><td>they are a lot</td><td>plus</td><td>little. References:</td><td>ISO</td>
13320 (2009) / ISO 14887.
Primary particle size
The carbon aggregates were cleaved by grinding in a grinding mill a carbon water dispersion (20% carbon, 5% wetting agent). The primary particle size is measured after different grinding times until the carbon aggregates are completely converted to the primary particles. The above PSD method that relates to determining the particle size distribution is also used to determine the primary particle size (wet dispersion).
Oxygen content
Oxygen mass fractions in solid samples are evaluated using the principles of inert gas fusion or solid carrier gas heat extraction. The sample is placed in a graphite crucible and inserted into an electrode furnace. The crucible is held between the upper and lower electrodes of a pulse furnace. A
IMPI
<img file="MX360762B_D0056.tif" />
High current passes through the crucible after purging with inert gas (He or Ar) creating an increase in temperature (above 2500 ° C). The gases generated in the furnace are released into the fluid from the inert gas stream. The gas stream is then sent to the appropriate infrared (O CÓ as by NDIR) or thermal conductivity (N and H by TCD detectors) for measurement. Instrument calibrations are performed using known reference materials.
PH value
A 1.5 g sample of charcoal is dispersed in distilled water with the help of a few drops of acetone and an ultrasonic treatment. The electrode of the calibrated pH meter is placed on the suspension. After a stabilization time of 2 minutes the suspension was stirred and the pH value was recorded in the nearest 0.05 unit. (ASTM D1512-95 (method B)).
<td colspan="2">Threaded density</td><td rowspan="2">powder</td><td rowspan="2">graphite</td><td rowspan="2">dry is poured</td>
<td>100 g</td><td>of</td>
<td>carefully</td><td>in</td><td>a cylinder</td><td>graduate.</td><td>Subsequently, the</td>
cylinder is fixed on the decentralized axis based pulsing machine and 1500 strokes are run. The reading
IMPI
<img file="MX360762B_D0057.tif" />
volume is taken and the density of the tap is calculated. Reference: -DIN-ISO 787-11.
Scott Density
Dry carbon powder is passed through the Scott voltmeter and collected below in a 16.39 cm<sup>3 </sup>(1 in<sup>3</sup>) container and weighed to the nearest 0.1 mg. Scott's density is calculated from the ratio of weight and volume. Reference: - ASTM B 329-98 (2003)
Oil absorption
The oil absorption test is a means of determining the general behavior of graphite and graphite-type materials with respect to liquid absorption. A slow filter paper is placed in a metal centrifuge tube that has an inner diameter of 13.5 mm and a sieve at the bottom (18 mesh). In order to wet the filter, 0.5 g of paraffinic oil is filled into the tube and centrifuged for 30 minutes at 521 g (1 g = 9.81 m / s<sup>2</sup>, corresponding to 1500 rpm in Sigma 6-10 centrifuge). After the wetting procedure, the tube is weighed and 0.5 g of graphite powder is added. The graphite is covered with 1 0.5 g of paraffinic oil and centrifuged for 521 g for 90 minutes. After centrifugation, the tube is weighed. Oil absorption per 100 g of
<img file="MX360762B_D0058.tif" />
of the base of the graphite powder increase is calculated on weight.
Oil Absorption Number
The oil absorption number test is a means of determining the general behavior of carbon black and carbon-type black materials in relation to liquid absorption. Paraffin oil is added by means of a burette at a constant speed to a drying (1 h at 125 ° C) carbon black sample in a mixing chamber of the Absorptometer. As the sample absorbs the oil, the mixture changes from a free-flow state to one of a semi-foot agglomeration, with an increase in viscosity. This increase in viscosity is transmitted to the torsional force detection system. When the viscosity reaches a predetermined torque level, the Absorptometer and buret will shut off simultaneously. The volume of added oil is read from the burette. The volume of oil per unit mass of carbon black is the oil absorption number. Reference: - ASTM D2414-01.
Ash content
A low walled ceramic crucible lights up
800 ° C in a muffle furnace and dried in a desiccator. A
IMPI
<img file="MX360762B_D0059.tif" />
10 g sample of dry powder (precision 0.1 mg) is weighed in a low walled ceramic crucible. The powder burns at a temperature of 815 ° C (1472 ° F) at a constant weight (at least 8 h). The residue corresponds to the ash content. It is expressed as a percentage of the initial weight of the sample. (DIN 51903 and DIN 51701 (division process)).
Metal concentration (for iron and lead in carbon samples)
This analysis is performed using a SDAR OES simultaneous emission spectrometer. The carbon powder, ground to a maximum particle size of 80 μιη by means of a vibrating mill, is compacted for one tablet. The sample is placed on the excitation support under argon atmosphere of the spectrometer. Subsequently, the fully automatic analysis can be started. Reference: (i) K. Slickers Automatic Emission Spectroscopy Brühl Druck und Presshaus Giessen (D) (1992), (ii) M. Wissler und P. Gebhardt Protokoll der 29. Sitzung des Unterausschusses Feststoffe im Arbeitskreis Kohlenstoff der Deutschen Keramischen Gesellschaft (12./13. Dez 1984)
Crystallite Size L<sub>to</sub>
L crystallite size<sub>to</sub> It is calculated from Raman measurements using the equation:
IMPI
<img file="MX360762B_D0060.tif" />
L<sub>to</sub> [Angstrom (A)] = C x (1<sub>G</sub>/1<sub>D</sub>) where the constant C has values of 44 [A] and 58 [A] for lasers with wavelengths of 514.5 nm and 632.8 nm,
<td colspan="6">respectively. I<sub>G</sub> and L<sub>D</sub> are the intensity of the peaks of</td>
<td>absorption G and respectively.</td><td>D-band</td><td>Raman</td><td>to 1580</td><td>cm<sup>-1</sup></td><td>and 132 0 cm '<sup>1</sup>,</td>
<td colspan="2">Crystallite size L_</td><td></td><td></td><td></td><td></td>
<td>The size</td><td>of the</td><td colspan="2">crystallites L<sub>c</sub></td><td>I know</td><td>determined by</td>
<td>analysis of</td><td>profiles</td><td colspan="2">diffraction</td><td> (002)</td><td>and (004). For</td>
In the present invention, the method suggested by Iwashita (N. Iwashita, C. Rae Park, H. Fujimoto, M. and M. Shiraishi Inagaki, Carbon 42, 701-714 (2004)) is used. The algorithm proposed by Iwashita has been developed specifically for carbon materials. The widths of the line profiles at half the maximum of the sample and the reference are measured. By means of a correction function, the width of the pure diffraction profile can be determined. The size of the crystallites is subsequently calculated by applying the Scherrer equation (P. Scherrer, Gottinger-Nachrichten 2 (1918) p.
98) .
Spacing between layers c / 2
IMPI
<img file="MX360762B_D0061.tif" />
The interlaminar space c / 2 is determined by X-ray diffractometry. The angular position of the maximum peak of the diffraction profiles (002) and are determined, by applying the Bragg equation, the spacing of the intermediate layer is calculated. The carbon sample is mixed with a silicon standard. A mixture of polyglycol and ethanol is added in order to obtain a highly viscous suspension. Subsequently, a thin layer of approx. 150 pm is applied to a glass plate and dried. A Cu Ka X-ray beam is used. Reference: Klug and Alexander, X-Ray diffraction Procedures John Wiley and Sons Inc., New York London (1967).
Graphitization degree
The degree of graphitization (P) with the meaning of the relative frequency (in percentage) of finding nearest neighbor layers ordered in an orientation of
<td>graphite is calculated as:</td><td>gives'<sup>P =</sup> aa '</td>
where d is the average intermediate layer separation measured according to the previous method, a 'is the intermediate distance for a random orientation (0.344 nm), and a is the distance for a graphite orientation (0.3354 nm). Reference: H. Takahashi Carbón 2 (1965) 432.
<img file="MX360762B_D0062.tif" />
Powder conductivity, compression, and compression work
A powder sample is pulsed into a mold and simultaneously a current passes through the sample through the anvil and die piston. The body of the womb is insulating. The pressure, force, thickness of the sample, and the voltage are measured while the compression of the sample. The specific resistivity is calculated as follows:
P (P) =
A · V (P) where p (P) is the specific resistivity as a function of pressure, A is the cross-sectional area of the samples, / is the applied current, V (P) is the established voltage difference , and t (P) is the thickness of the sample. For comparison purposes p (P) is reported as a function of the sample density calculated as follows:
ρ (Ρ) = where p (P) is the density of the sample and m is its mass. The mechanical work for compression is calculated as i
AND <sup>=</sup>'^ ipjS (hj_<sub>]</sub> - hj) and- «
II> f <1 IICRg W * 7. * lL · · - ·
<img file="MX360762B_D0063.tif" />
where E is the mechanical compression work, p is the pressure, S is the cross-sectional area and h is the thickness (N. Probst, E. Grivei, Carbón 40 (2002) 201-205).
Lead impregnation
A 10 wt% carbon dispersion in 1M aqueous Pb (NÜ3) 2 is stirred for 24 h. It is then filtered and the remaining carbon is repeatedly washed with deionized water and then dried. BET surface area and Pb content are measured on dry carbon according to the methods described above.
Immersion Potential
The potential electrochemistry of a bonded carbon-based electrode immersed in a 1M aqueous Pb (NÜ3) 2 solution measured against a Hg / Hg (SO4) /3.8MH2SO4 reference electrode (potential vs NHE 634mV). The value given is an average during the first minute of immersion.
Lead deposition
An electrochemical cell using a carbon based electrode attached according to the working electrode, a Hg / Hg reference electrode (SO<sub>4</sub>) /3.8MH<sub>2</sub>SW<sub>4</sub> and a counter electrode is assembled using 1M aqueous Pb (NC> 3) 2 as the electrolyte. A potentiostatic pulse ls at -1.5 V vs the
<img file="MX360762B_D0064.tif" />
IMPI reference electrode is applied after 60s of equilibrium time at the open circuit potential. The working electrode is supported in the potential open circuit for 60s after the potentiostatic pulse and then carefully washed in deionized water and dried. The dry electrode was observed with a scanning electron microscope to visualize possible lead deposition.
Powder conductivity of mixtures
The resistivity of mixtures of carbon and other material is measured according to the previous method. Pressure resistivities of 4.5 kNcm<sup>2</sup> for different mixtures they are represented graphically as a function of carbon concentration.
Double layer capacitance
Cyclic voltammetries are measured at 1 MH bonded carbon electrodes<sub>2</sub>S0<sub>4</sub> electrolyte in a three-electrode arrangement with a Hg / Hg reference electrode (SO<sub>4</sub>) /3.8MH2SO4 and a counter electrode. Cyclic voltammetries are measured in the 0.1-0.5V -vs potential range. reference electrode in order to avoid faradic reactions at the sweep rate of 1 mV / s. The specific double layer capacitance is derived from the
<img file="MX360762B_D0065.tif" />
average absolute current in the potential range 0 --0.4V as follows:
s · m where C is the specific capacitance, \ i \ is the average absolute current in the potential range 0 - 0.1V, s is the sweep speed, and m is the mass of active material of the tested electrode.
Hydrogen evolution
Cyclic voltammetries are measured at the 1 MH2 SO4 electrolyte bound carbon electrodes in a three electrode arrangement with a Hg / Hg (S04) /3.8MH2SO4 reference electrode and a counter electrode. Cyclic voltammetries are measured in the 0.1 - -1.2V potential range vs. reference electrode. H<sub>2</sub> evolves to a potential of ca. -0.8V For the considered systems. The position involved in evolution H<sub>2</sub> it is calculated as follows:
<2 =
<img file="MX360762B_D0066.tif" />
- c - 0.6 where Q is the specific charge involved in the evolution H<sub>2</sub>, i is the current, m is the mass of active material in the electrode, t is the time, and C is the specific capacitance. The reduction charge is calculated at
<img file="MX360762B_D0067.tif" />
from the cyclic voltammetry in the potential range of 0.6 - -1.2V. From the calculated load value, the load required to load the double layer (C 0.6) is subtracted.
Elastic Recovery
Elastic recovery is a source of information regarding the recoverability of compacted graphite powders. A defined amount of powder is poured into a mold. After inserting the blow and sealing the die, air is evacuated from the die. A compression force of about 1500 kg / cm<sup>2</sup> I know
<td>apply and</td><td>I know</td><td colspan="2">records the height of</td><td>powder. This height</td><td>I know</td>
<td>registers</td><td>of</td><td>new after</td><td>of what</td><td>has been released</td><td>the</td>
<td>Pressure.</td><td>The</td><td>Recovery</td><td>elastic</td><td>It's the difference</td><td>of</td>
height as a percentage of the height under pressure.
Having now described the various aspects of the present invention in general terms, it will be apparent to those skilled in the art that many modifications and variations are possible without departing from the object and scope of the present invention. Some modalities will now be described by way of illustration, with reference to the following numbered modalities and working examples.
<img file="MX360762B_D0068.tif" />
one. Hybrid surface-modified carbon particles comprising a graphite core coated with amorphous agglomerate carbon have a BET surface area of at least 50 m<sup>2</sup>/ g, or at least 80 m<sup>2</sup>/ g, or at least 100 m<sup>2</sup>/ g and none greater than 800 m<sup>2</sup>/ g and a DFT mesopore area of at least 40 m<sup>2</sup>/ g, or at least 60 m<sup>2</sup>/ g, or at least 70 m<sup>2</sup>/ g, or at least 80 m<sup>2</sup>/ g and not greater than 400 m<sup>2</sup>/ g.
2. The modality hybrid carbon particles
1, where the ratio of the DFT mesopore area to the total DFT pore area is 20 to 90%, or 45-75%, or 50 to 70% of modified surface.
3. Modified surface carbon hybrid particles of mode 1 or mode 2, where the volume of DFT mesopores is at least 0.10 cm<sup>3</sup>/ g, or at least 0.17 cm<sup>3</sup>/ g, or at least 0.29 cm <sup>3</sup>/ g.
Four. The modified surface carbon hybrid particles of Modes 1 to 3, wherein the ratio of DFT mesopore volume to total DFT pore volume is 50 to 95%, or 70 to 95%. 5. Hybrid particles of modified surface carbon of modalities 1 to 4, · where the agglomerates have a D value<sub>90</sub> (as determined by the wet dispersion method) between 20 and 60 pm, or between 30 and 50 pm, or between 40 and 50 pm and / or a D value<sub>5</sub>or from 7 to 15 pm, or from 7 to 12 pm and / or a Dio value of 0.3-4 pm, or 0.4-3 pm, or from 0.5 to 2 and pm / or a D value<sub>90</sub> (how I know
<img file="MX360762B_D0069.tif" />
determined by the dry dispersion method), from 50 to 300 μιη, or from 100 to 300 pm, or from 100 to 200 pin, or 150-200 pm.
6. Hybrid particles of surface modified carbon of modalities 1 to 5, where the oxygen content is at least 0.45% w / w, or at least 0.85% w / w, or at least 1% w / w, or at least 2% w / w, or at least 3% w / w.
7. Modified surface carbon hybrid particles of Modalities 1 to 6, wherein the pH of the particles is less than 7.0, or below 6.5, or below or 6.0, or below or 5.0.
8. Modified surface carbon hybrid particles of modalities 1 to 7, where the compacted density is 0.35 to 0.7 g / cm<sup>3</sup>, or 0.4-0.7 g / cm<sup>3</sup>, and / or in which the Scott density is 0.2 to 0.6 g / cm <sup>3</sup>, or from 0.25 to 0.6 g / cm<sup>3</sup>.
9. The modified surface carbon hybrid particles of modalities 1 to 8, where the oil absorption is 150% w / w or less, or 140% w / w or less, or 120% w / w or less, or 100% w / w po less, or 80% p / p less.
10. The modified surface carbon hybrid particle of modalities 1 to 9, where the ash content is less than 0.1%, or below 0.08%, or below 0.05%.
eleven. Hybrid particles of modified surface carbon of modalities 1 to 10, where the value of
<img file="MX360762B_D0070.tif" />
Fe content is less than 500 ppm, or below 400 ppm, or below 300 ppm, or below 200 ppm, or below 160 ppm.
12. Hybrid particles of modified surface carbon of modalities 1 to 11, where the size of the crystallites L<sub>to</sub> (measured by Raman spectroscopy) is 1 to 10 nm, or 3 to 8 nm, or 4 to 6 nm.
13. Hybrid particles of surface modified carbon from modality 1 to 12, where the size of the crystallites L<sub>c</sub> (as measured by XRD) is 10 to 100 nm, or 10 to 60 nm, or 10 to 50 nm.
14. Hybrid particles of modified surface carbon of modalities 1 to 13, where the degree of graphitization is 80 to 95%, or 85 to 95%, or 90 to 95%.
fifteen. Hybrid particles of surface modified carbon of modalities 1 to 14, where the Dgo value of non-agglomerated particles (as determined by the wet dispersion method) is less than 10 μιη, or less than 8 pm, or less of 5 pm, or less than 4 pm, or less than 3 pm, or less than 2 pm, or less than 1.8 pm and / or in which value D<sub>50 </sub>of non-agglomerated particles is less than 4 pm, or less than 2 pm, or less than 1 pm, or less than 0.75 pm, or less than 0.4 pm, or less than 0.3 pm and / or in which the Dio value of particles not agglomerates is less than 0.6 pm, or less than 0.4 pm, or less than 0.2 pm, or less than 0.15 pm.
ιτ-a
IMPI MEXICAN INSTITUTE OF LA MONEDAD INDUSTRIAL
<img file="MX360762B_D0071.tif" />
16. A method of manufacturing surface modified carbon hybrid particles as defined in any one of embodiments 1 to 15, comprising the steps of; a) grinding graphite in a gas-tight sealing mill; b) functionalization of the resulting hybrid carbon by controlled oxidation.
17. The method of modality 16, where step a) is carried out until the value D<sub>90</sub> of non-agglomerated particles (as determined by the wet dispersion method) is less than 10 μπι, or less than 8 pm, or less than 5 pm, or less than 4 pm, or less than 3 pm, or less than 3 pm, or less than 1.8 pm and / or in which the D value<sub>5</sub>or of non-agglomerated particles is less than 4 pm, or less than 2 pm, or less than 1 pm, or less than 0.75 pm, or less than 0.4 pm, or less than 0.3 pm and / or in which Dio value of particles uncrowded is less than 0.6 pm, or less than 0.4 pm, or less than 0.2 pm, or less than 0.15 pm.
18. The method of modalities 16 or 17, wherein the product from step a) is kept in the gas-tight sealed mill for at least 15 minutes, or at least 30 minutes, or at least 45 minutes before carrying out the stage b).
19. The method of modality 18, wherein the product of step a) is carried out in the gas-tight sealed mill up to the value D<sub>90</sub> (as determined ί '•' S.
IMPI
INSTITUTO MEXICANO DE LA MONEDAD iNDurnuAL
<img file="MX360762B_D0072.tif" />
by the wet dispersion method) of between 20 and 60 μπι, or 30 to 50 pin, or 40 to 50 pm and / or a D50 value of 7 to 15 pin, or 7 to 12 pin and / or a value D<sub>i0</sub> from 0.3-4 pm, or 0.4-3 pin, or from 0.5 to 2 pm and / or a D value<sub>90</sub> (as determined by the dry dispersion method), from 50 to 300 pm, or from 100 to 300 pm, or from 100 to 200 pm, or 150-200 pm.
twenty. The method of modalities 16 to 19, wherein the controlled oxidation is carried out by stirring the particles obtained in step a) in a mixer.
twenty-one. The method of modalities 16 to 20, wherein the controlled oxidation is carried out at a temperature not greater than 400 ° C, or not greater than 300 ° C, or not greater than 200 ° C, or not greater than 100 ° C, or not greater than 50 ° C, or not greater than 30 ° C.
22. The method of modalities 16 to 21, where the controlled oxidation is carried out until the oxygen content is at least 0.45% w / w, or at least 0.85% w / w, or at least 1% w / w p.
2. 3. The method of modalities 16 to 22, wherein controlled oxidation is carried out until the pH is below 7.0, or below 6.5, or below 6.0, or below 5.0.
24. The method of modalities 16 to 23, where the controlled oxidation is carried out in the presence of air,
<img file="MX360762B_D0073.tif" />
moisture, oxygen, other oxidizing gas and / or an oxidizing liquid.
25. The method of modality 24, where the oxidizing gas is N0<sub>x</sub>, ozone or carbon dioxide.
26. The method of modality 24, wherein the oxidizing liquid is hydrogen peroxide or nitric acid.
27. The method of modalities 16 to 26, wherein the sealing mill is a ball mill, such as a rotary mill, a tumbling mill, or a vibration mill.
28. The method of modalities 16 to 27, wherein the mill chamber is equipped with an internal lining.
29. The method of modalities 16 to 28, where the ceramic balls are used in step a).
30. The method of modalities 16 to 29, wherein step a) is carried out for not more than 150 hours, or not more than 96 hours, or not more than 84 hours, or not more than 72 hours or not more than 60 hours.
31. The method of modalities 16 to 30, where after step b) the product is dispersed in a liquid in the presence of a surfactant or a polymeric compound by applying shear force to deagglomerate the particles.
32. Hybrid particles of surface modified carbon as defined in either modality
<img file="MX360762B_D0074.tif" />
to 15, obtainable by the method as defined in any of the modalities 16 to 31.
33. A mixture of the surface modified carbon hybrid particles according to either mode 1 to 15 or mode 32, and lignosulfonates and / or barium sulfate as an additive to the negative electrode of lead acid batteries.
3. 4. A battery electrode comprising the surface modified carbon particles of either mode 1 to 15 or mode 32, or the mixture of mode 33 as a conductive additive.
35. The embodiment 34 battery electrode, wherein the barium sulfate is added in an amount of from about 0.2 to about 2% by weight of the total mass of the electrode.
36. The battery electrode of embodiment 34 or 35, wherein the lignosulfonates are added in an amount of about 0.1 to about 10.5% by weight of the total mass of the electrode.
37. A polymer compound filled with the surface-modified carbon particles of either Mode 1 to 15 or Mode 32.
38. The use of the battery electrode of any of the modalities 34 to 36 in lead acid batteries.
<img file="MX360762B_D0075.tif" />
39. The use of the modality battery electrode in sulfur lithium batteries.
40. The use of modality 34 battery electrode in double-layer electrochemical capacitors.
41. Use according to modality 38, where the double-layer electrochemical capacitors have an average capacitance above 7F / g, or above 6 F / g, or above 5.5 F / g.
42. Use of the surface modified carbon particles of any of the modalities 1 to 15 or 32 as the carbon supports modality.
43. A dispersion of the surface-modified carbon particles of either Mode 1 to 15 or Mode 32 in a liquid in the presence of a surfactant.
44. Use of the surface modified carbon particles of either modality 1 to 15 or modality 32 to form a dispersion in a liquid in the presence of a surfactant by applying shear force to deagglomerate the particles.
Four. Five. Use of the dispersion of modality 40 or 41 as a conductive coating.
EXAMPLES
<img file="MX360762B_D0076.tif" />
Example 1 - Method for Preparation of Modified Surface Carbon Hybrid Particles
The raw synthetic graphite with the finest grain size distribution of 20-30mm and preferably finest of 1mm was loaded into a vibratory ball mill (type Vibratom SM 125 by Siebtechnik-Germany) filled by volume of about 70-80% with steel balls with a diameter of approximately 50 mm for a total weight of 1400 kg. The amount of graphite loaded corresponds to a ratio of graphite media to grinding of around 16-20. The vibrating tube mill was gas-tight sealed and the (dry) grinding process was carried out in the gas-tight grinding chamber of the vibrating ball mill. After finishing the grinding process, the soil carbon was rested for approximately 0.5 h in the sealed grinding chamber (airtight) and then transferred to an intensive batch mixer (Eirich, Germany 75 L batch size) for the process functionalization. The carbon material was gently stirred in contact with air for a minimum of 1 h without any heating (i.e. from room temperature, although the mixture is heated due to the exothermic reaction), resulting in hybrid carbon particles surface modified (also referred to herein as hybrids
IMPI
<img file="MX360762B_D0077.tif" />
carbon) that are characterized by the following parameters.
Table 1:
<td>Carbon Hybrid</td><td>Grinding Time [h]</td><td>BET SSA [m<sup>2</sup>/ g]</td><td>Area of Mesoporos [m<sup>2</sup>/ g]</td><td>Groups Oxygen Surface weight]</td><td>dd [% n</td>
<td>TO</td><td> 5</td><td> 107</td><td> 74</td><td colspan="2"> 0.87</td>
<td>B</td><td> 10</td><td> 224</td><td> 129</td><td colspan="2"> 1.3</td>
<td>C</td><td> 16.5</td><td> 290</td><td> 165</td><td colspan="2"> 1.6</td>
<td>D</td><td> 32</td><td> 431</td><td> 227</td><td colspan="2"> 3.4</td>
<td>AND</td><td> 48</td><td> 501</td><td> 249</td><td colspan="2"> 4.1</td>
The carbon hybrids obtained according to Example 1 were further characterized and compared to other carbon materials, such as synthetic graphite (TIMREX® SFG6-TIMCAL graphite and carbon), expanded graphite (TIMREX® BNB90 - TIMCAL graphite and carbon) , black carbon (ENSACO® 350G -TIMCAL graphite and carbon), and activated carbon (YP50F - Kuraray Chemical Co.):
Table 2:
<td>Carbon Material</td><td>Oxygen content [%]</td><td>PH</td><td>BET surface area [m / g]</td>
<td>Carbon Hybrid A</td><td> 0.87</td><td> 5.1</td><td> 107</td>
<td>Carbon C Hybrid</td><td> 1.6</td><td> 4.7</td><td> 290</td>
<td>Carbon Hybrid D</td><td> 3.4</td><td> 4.5</td><td> 431</td>
<td>Carbon Black</td><td> 0.41</td><td> 10</td><td> 800</td>
<td>Synthetic graphite</td><td> 0.16</td><td> 5.4</td><td> 16</td>
<td>Expanded graphite</td><td> 0.32</td><td> 5.9</td><td> 24</td>
IMPI
<img file="MX360762B_D0078.tif" />
Table 3:
<td>Carbon Material</td><td>Oil Absorption (¾)</td><td>Elastic Recovery (%)</td>
<td>Carbon Hybrid A</td><td> 79</td><td> 14</td>
<td>Carbon Hybrid B</td><td> 93</td><td> 18</td>
<td>Carbon Hybrid C</td><td> 102</td><td><sup>18</sup></td>
<td>Carbon Hybrid D</td><td> 110</td><td> 19</td>
<td>Carbon Hybrid E</td><td> 120</td><td> 17</td>
<td>Carbon Black</td><td> >600</td><td> 88</td>
<td>Synthetic Graphite</td><td> 175</td><td> 11</td>
<td>Activated Carbon</td><td> 155</td><td> 75</td>
<td>Expanded graphite</td><td> 166</td><td> 11</td>
Table 4t
<td>Carbon Material</td><td>The [nm]</td><td>LC [nm]</td><td>c / 2 [nm]</td><td>Graphitization grade P [%]</td><td>Compacted Density [g / cm<sup>3</sup>]</td>
<td>Carbon Hybrid A</td><td> 5.7± 0.5</td><td> 53</td><td> 0.3361</td><td> 92</td><td> 0.676</td>
<td>Carbon Hybrid B</td><td> 4.8± 0.3</td><td> 41</td><td> 0.3361</td><td> 92</td><td> 0.641</td>
<td>Carbon Hybrid D</td><td> 4.9± 0.8</td><td> 18</td><td> 0.3370</td><td> 83</td><td> 0.431</td>
<td>Expanded graphite</td><td> 24.3±10. 5</td><td> 40</td><td> 0.3360</td><td> 93</td><td> 0.079</td>
<td>Synthetic Graphite A</td><td> 24.9±1.1</td><td> 175</td><td> 0.3357</td><td> 97</td><td> 0.12</td>
<td>Activated Carbon</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0.305</td>
<td>Synthetic Graphite B</td><td> —</td><td> -</td><td> -</td><td> 99</td><td> -</td>
IMPI
<img file="MX360762B_D0079.tif" />
Table 5:
<td>Carbon Material</td><td>Average Capacitance F / g</td><td>BET SSA (m7g)</td>
<td>Carbon Hybrid A</td><td> 7.5</td><td> 110</td>
<td>Carbon Hybrid B</td><td> 20.1</td><td> 220</td>
<td>Carbon C Hybrid</td><td> 25.1</td><td> 275</td>
<td>Carbon Hybrid D</td><td> 58.7</td><td> 419</td>
<td>Carbon Hybrid E</td><td> 58.3</td><td> 481</td>
<td>Expanded graphite</td><td> 4.4</td><td> 24</td>
<td>Carbon Black</td><td> 20.6</td><td> 753</td>
<td>Synthetic Graphite</td><td> 4.9</td><td> 9</td>
<td>Activated Carbon</td><td> 198</td><td> 1473</td>
Table 6: Mesoporo and Micropore surface area (see figure 4)
<td></td><td>Area BET (m7g)</td><td>Area DFT (»7g)</td><td>Area of Micropore (m '/ g)</td><td>Area of Micropore (%)</td><td>Area d Mesoporo (m '/ g)</td><td>Area of Mesoporo (%)</td>
<td>Carbon Hybrid A</td><td> 107</td><td> 105</td><td> 31</td><td> 30</td><td> 74</td><td> 70</td>
<td>Carbon Hybrid B</td><td> 224</td><td> 223</td><td> 94</td><td> 42</td><td> 129</td><td> 58</td>
<td>Carbon C Hybrid</td><td> 290</td><td> 288</td><td> 123</td><td> 43</td><td> 165</td><td> 57</td>
<td>Carbon Hybrid D</td><td> 431</td><td> 431</td><td> 204</td><td> 47</td><td> 227</td><td> 53</td>
<td>Carbon Hybrid E</td><td> 501</td><td> 505</td><td> 256</td><td> 51</td><td> 249</td><td> 49</td>
<td>Carbon Black</td><td> 809</td><td> 777</td><td> 357</td><td> 46</td><td> 420</td><td> 54</td>
<td>Expanded graphite</td><td> 30</td><td> 44</td><td> 0</td><td> 0</td><td> 44</td><td> 100</td>
<td>Activated Carbon</td><td> 1382</td><td> 1854</td><td> 1659</td><td> 89</td><td> 195</td><td> 11</td>
IMPI
<img file="MX360762B_D0080.tif" />
Table 7; Mesopore and Micropore volume (see figure
5)
<td></td><td>DFT pore volume (cm<sup>2</sup>/ g)</td><td>Micropore volume (cm<sup>2</sup>/ g)</td><td>Micropore volume (*)</td><td>Volume of Mesopore (cm<sup>2</sup>/ g)</td><td>Mesoporo volume (%)</td>
<td>Hybrid of Carbon A</td><td> 0.187</td><td> 0.014</td><td> 8</td><td> 0.173</td><td> 93</td>
<td>Hybrid of Carbon B</td><td> 0.315</td><td> 0.042</td><td> 13</td><td> 0.273</td><td> 87</td>
<td>Hybrid of Carbon C</td><td> 0.405</td><td> 0.055</td><td> 14</td><td> 0.350</td><td> 86</td>
<td>Hybrid of Carbon D</td><td> 0.557</td><td> 0.090</td><td> 16</td><td> 0.466</td><td> 84</td>
<td>Hybrid of Carbon E</td><td> 0.615</td><td> 0.113</td><td> 18</td><td> 0.503</td><td> 82</td>
<td>Black Carbon</td><td> 0.979</td><td> 0.166</td><td> 17</td><td> 0.813</td><td> 83</td>
<td>Expanded graphite</td><td> 0.142</td><td> 0</td><td> 0</td><td> 0.142</td><td> 100</td>
<td>Activated Carbon</td><td> 0.791</td><td> 0.603</td><td> 76</td><td> 0.188</td><td> 24</td>
The following table shows the data obtained for the carbon D hybrid before and after the functionalization step (controlled oxidation).
<img file="MX360762B_D0081.tif" />
Table 8¾
IMPI MEXICAN INSTITUTE OF INDUSTRIAL MONEDAD
<img file="MX360762B_D0082.tif" />
<td>Carbon Hybrid D</td><td>Before</td><td>of</td><td>the</td><td>After</td><td>the</td>
<td></td><td colspan="2">functionalization</td><td></td><td>functionalization</td><td></td>
<td></td><td>(oxidation)</td><td colspan="2">but</td><td>(oxidation in the</td><td>air</td>
<td></td><td>then</td><td></td><td>of the</td><td colspan="2">in RT in a mixer</td>
<td></td><td colspan="2">storage in</td><td>the</td><td colspan="2">intensive for 3</td>
<td></td><td>air in RT</td><td>during</td><td> 24</td><td colspan="2">h, measured temperature</td>
<td></td><td>h</td><td></td><td></td><td>in sample 140</td><td>° C)</td>
<td>Oxygen content [wt. %]</td><td colspan="3"> 0.21</td><td colspan="2"> 3.4</td>
<td>c / 2 [nm]</td><td colspan="3"> 0.3367</td><td colspan="2"> 0.337</td>
<td>L „[nm]</td><td colspan="3"> 20</td><td colspan="2"> 18</td>
<td>L. [nm]</td><td colspan="3"> 5.8</td><td colspan="2"> 4.9</td>
<td>Graphitization (factor P)</td><td colspan="3"> 85</td><td colspan="2"> 83</td>
<td>BET [g cnT]</td><td colspan="3"> 389</td><td colspan="2"> 419</td>
<td>My crop area [rrf g 'Ί</td><td colspan="3"> 192</td><td colspan="2"> 204</td>
<td>Mesoporo area [m<sup>4</sup> g<sup>1</sup>]</td><td colspan="3"> 205</td><td colspan="2"> 227</td>
<td>Micropore area [cm<sup>4</sup></td><td colspan="3"> 0.052</td><td colspan="2"> 0.055</td>
<td>Mesoporo area [cm<sup>4</sup> g '</td><td colspan="3"> 0.326</td><td colspan="2"> 0.350</td>
<td>Particle size distribution (Laserdiffraction MALVERN Mastersizer S) Dry dispersion of particles in a DUST FEEDER IN</td><td> 2.3</td><td></td><td></td><td> 2.1</td><td></td>
<td>SECO MALVERN MSX64)</td><td> 18.7</td><td></td><td></td><td> 15.8</td><td></td>
<td>D<sub>10</sub> [p.m] OR<sub>50</sub> (P.m] D,<sub>or</sub> [p.m]</td><td> 183.8</td><td></td><td></td><td> 147.9</td><td></td>
<td>Wet dispersion</td><td> 1.1</td><td></td><td></td><td> 1.1</td><td></td>
<td>(5 min. Of treatment</td><td> 10.9</td><td></td><td></td><td> 10.9</td><td></td>
<td>ultrasonic)</td><td> 44.8</td><td></td><td></td><td> 43.1</td><td></td>
<td>Dio CP<sup>1</sup>] D<sub>SW</sub> [p.m] D<sub>or</sub>„[Pm]</td><td></td><td></td><td></td><td></td><td></td>
Example 2 - Alternative Method for the Preparation of
Hybrid Particles of Modified Surface Carbon
The raw synthetic graphite with the finest grain size distribution of 2 0-30 mm and preferably
<img file="MX360762B_D0083.tif" />
IMPI finer than 1mm was loaded into a vibratory ball mill (type Vibratom SM 125 by Siebtechnik-Germany) at volume filling of about 70-80% with steel balls with a diameter of about 50mm for a total weight 1400 kg. The amount of graphite loaded corresponds to a ratio of graphite media to grinding of about 15. The vibratory ball mill was gas-tight sealed and the (dry) grinding process was carried out in the gas-tight grinding chamber of the vibratory ball mill. After the graphite was ground for 96 hr, the soil carbon was rested for approximately 0.5 hr in the sealed (airtight) grinding chamber and then transferred to an intensive batch mixer (Eirich, Germany 75 L batch size) for the functionalization process. The functionalization of the resulting carbon material is performed by gently stirring the carbon material in the batch mixer flooded by a gas mixture containing 10% oxygen in nitrogen and 90% relative humidity for 3 h. The resulting hybrid carbon showed a BET SSA of 720 m<sup>2</sup>/ g a mesopore area vs. total DFT area ratio of 45%.
Example 3 - Additional Alternative Method for Preparation of Modified Surface Carbon Hybrid Particles
<img file="MX360762B_D0084.tif" />
The raw natural graphite with 50-mesh grain size distribution was loaded into a vibratory ball mill (type Vibratom SM 125 by Siebtechnik Germany) filled in volume of about 70-80% with steel balls with a diameter of approximately 50 mm for a total weight of 1400 kg. The amount of graphite loaded corresponds to a ratio of graphite media to grinding of about 20. The vibratory ball mill was gas-tight sealed and (dry) the grinding process was carried out in the gas-tight grinding chamber of the vibratory ball mill. After the graphite was ground for 20 hr, the soil carbon rested for approximately 0.5 hr in the grinding chamber they were sealed and then transferred to an intensive batch mixer (Eirich, Germany 75 L batch size) for the functionalization process. Functionalization of the resulting carbon material is accomplished by gently stirring the carbon material in the air-flooded batch mixer for 1 hr. The resulting hybrid carbon showed a SSA BET of 330m<sup>2</sup>/ g and an area of mesopores vs. Total DFT area ratio of about 56%.
Example 4 - Additional Alternative Method for
Preparation of Modified Surface Hybrid Carbon Particles
IMPI
<img file="MX360762B_D0085.tif" />
The same unprocessed synthetic graphite materials same as that described in Example 1 were loaded into a drum (or tumbling) ball mill with a chamber volume of about 43 liters and a chamber diameter of 400 mm fill in volume of about 20-30% with steel balls with a diameter of about 30 mm for a total weight of 50 kg. The amount of graphite (batch) loaded corresponds to a ratio of graphite media to grinding around 2030. The grinding process was carried out in the hermetic sealed grinding chamber of the rotating mill (rot. Speed = 50-80 rpm) for a total duration of 5, 16, 32 and 48 h depending on BET selectivp that cause a hybrid carbons with a BET SSA of approximately 100, 300, 400 and up to 500 m<sup>2</sup>/ g, respectively after the functionalization process that was done in the intensive batch mixer flooded with air for 1 h. The grinding time, graphite batch, medium type grinding, size and shape, together with the mill filling and the weight ratio are the process parameters that allow adjusting the final properties of the products, that is, the area of BET surface, PSD, Scott density.
Example 5 - Additional Alternative Method for the Preparation of Hybrid Surface Carbon Particles
Modified
<img file="MX360762B_D0086.tif" />
The surface modified carbon hybrid particles were produced according to the procedures described in Example 1 and 3, but prior to starting the grinding process, the grinding chamber was purged with an inert gas stream (typically nitrogen or argon) . Purge gas flow and time were selected in order to minimize the amount of air trapped in the grinding chamber. The efficiency of the process could be improved by more than 10% in terms of reducing grinding time. You can also apply other media
<td>of me j ora de</td><td>the</td><td>efficiency</td><td>purge,</td><td>how</td><td>the</td>
<td>establishment</td><td>of the</td><td>camera of</td><td>grinding on</td><td>brief</td><td>in</td>
<td>movement.</td><td></td><td></td><td></td><td></td><td></td>
<td>Ex shipping 6</td><td>Method</td><td>Alternative</td><td>Additional</td><td>for</td><td>the</td>
Preparation of Modified Surface Carbon Hybrid Particles
The hybrid carbon particles were produced according to the procedures described in Example 1 and 3, but the grinding chamber was in this case equipped with an internal lining in order to reduce (metal) contamination of the product. Ceramic, rubber, polymer or other type of material can be used for the aforementioned coating. Ceramic grinding media, zr0<sub>2</sub>, or AI2O3 can also be
IMPI
<img file="MX360762B_D0087.tif" />
use for the same purpose. The surface modified carbon hybrid particles obtained using the aforementioned mill produced products having similar BET surface area, PSD content and mesopores, although slightly longer grinding times are required in some cases compared to iron or grinding media stainless steel. Grinding with non-metallic grinding media did not lead to any increase in contamination by metals such as iron, nickel, molybdenum and vanadium. In fact, the iron content of the obtained particles was well below 50 ppm or less (depending on the purity of the starting material).
Example 7 - Preparation of a Colloidal Aqueous Dispersion of Hybrid Modified Surface Carbon Particles kg of the sample from D (as obtained from Example 1) was mixed with 384 kg of water containing 37 kg of an alkyl polyglycol ether Ci<sub>6</sub> -C<sub>8</sub> (OC2H<sub>5</sub>)<sub>n</sub>, where n = 25 and 3 kg of 25% aqueous ammonia using a solvent (power: 44 kW, stirring time 1 h). The aqueous premix was then further treated in an attrition mill (power: 55 kW) for 6 hr up to a viscosity of 1300 mPas (at 10 1 / s) and a D<sub>50</sub> from 0.7 pm, and a D <sub>90</sub> from 2.5 pm it was reached.
IMPI
<img file="MX360762B_D0088.tif" />
Contents61
93 sheets
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25 members in 14 offices
Priority claims11
| Document | Office | Kind | Date |
|---|---|---|---|
| 12168742 | European Patent Office (EPO) | A | |
| 121687420 | European Patent Office (EPO) | – | |
| 201261649412 | United States of America | P | |
| 61649412 | United States of America | – | |
| 2013055370 | European Patent Office (EPO) | W | |
| 121687420 | – | – | – |
| 61649412 | – | – | – |
| EP20120168742 | – | – | – |
| PCTEP2013055370 | – | – | – |
| US201261649412P | – | – | – |
| WO2013EP55370 | – | – | – |
Members25
| Document | Office | Kind | |
|---|---|---|---|
| CA2872715A1 | Canada | A1 | |
| WO2013174536A1 | World Intellectual Property Organization (WIPO) | A1 | |
| CN104271502A | China | A | |
| EP2852554A1 | European Patent Office (EPO) | A1 | |
| US2015099180A1 | United States of America | A1 | |
| KR20150059137A | Republic of Korea | A | |
| MX2014014227A | Mexico | A | |
| JP2015525184A | Japan | A | |
| CN104271502B | China | B | |
| CN106082203A | China | A | |
| BR112014029026A2 | Brazil | A2 | |
| JP6235569B2 | Japan | B2 | |
| EP2852554B1 | European Patent Office (EPO) | B1 | |
| DK2852554T3 | Denmark | T3 | |
| ES2663004T3 | Spain | T3 | |
| NO2870515T3 | Norway | T3 | |
| US9991016B2 | United States of America | B2 | |
| PL2852554T3 | Poland | T3 | |
| US2018254119A1 | United States of America | A1 | |
| HUE038545T2 | Hungary | T2 | |
| US10115493B2 | United States of America | B2 | |
| MX360762BThis record | Mexico | B | |
| CN106082203B | China | B | |
| KR102069120B1 | Republic of Korea | B1 | |
| CA2872715C | Canada | C |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 360762
- Publication, DOCDB
- 360762
- Publication, EPODOC
- MX360762
- Application
- 2014014227
- Application, DOCDB
- 2014014227
- Application, EPODOC
- MX20140014227
Titles
- Spanish
- PARTICULAS HIBRIDAS DE CARBONO DE SUPERFICIE MODIFICADA, METODOS DE REALIZACION Y APLICACIONES DE LAS MISMAS.
Classification
- CPC, 14
- H01G11/24
- H01B1/04
- H01G11/42
- H01M4/625
- H01M4/627
- C01B32/21
- Y02E60/10
- H01B13/0026
- H01G11/26
- H01M4/133
- H01M4/366
- H01M4/583
- H01M4/587
- Y02E60/13
- IPC, 4
- C01B32 20
- C01B32 15
- H01G11 42
- H01M4 583