High structure, medium surface area carbon black with low microporosity and optimized mesoporosity

Abstract

The present invention relates to carbonaceous particulate materials having an optimized Braun-Emmet-Teller specific surface area (BET SSA), pore size distribution, crystallinity and aggregate structure, which have advantageous properties such as, for example, high corrosion resistance and improved mass transfer properties, which make them particularly useful as support materials for catalysts in fuel cells or electrolytic cells.

Description

Technical Field

[0001] The present invention relates to carbonaceous particulate materials having optimized Braun-Emmett-Teller specific surface area (BET SSA), pore size distribution, crystallinity, and aggregate structure, which have advantageous properties such as, for example, high corrosion resistance and improved mass transport characteristics, making them particularly suitable as support materials for catalysts in applications requiring such properties, such as, for example, fuel cells or electrolyzers.

[0002] This document also provides catalyst compositions and catalyst layers, which, for example, can be used as catalysts in electrochemical applications. Furthermore, fuel cells and electrolyzers comprising the advantageous carbonaceous particulate material according to the invention are provided. Finally, this document provides a method for producing the advantageous carbonaceous particulate material according to the invention. Background Technology

[0003] Fuel cells are a field of clean power generation systems that have garnered significant attention not only from the scientific community but also from the public and industry, due to their relatively low environmental impact. In a fuel cell, the energy from the chemical reaction between hydrogen (H2) and oxygen (O2) (usually supplied as air) is electrochemically converted into electricity. Therefore, in principle, the only byproduct generated during operation is water. The most common type of fuel cell used in vehicle applications is the proton exchange membrane fuel cell (PEMFC).

[0004] A PEM fuel cell typically comprises an anode (“fuel electrode”) and a cathode (“air electrode”), sandwiched between a gas diffusion layer (GDL), followed by a microporous layer (MPL) and a catalyst layer, separated by a central electrically insulating proton exchange membrane, which is typically composed of a Nafion-based material (sulfonated tetrafluoroethylene fluorinated copolymer). During fuel cell operation, a continuous stream of hydrogen fuel flows through the anode, while a continuous stream of air flows through the cathode. This causes the hydrogen to be oxidized by the catalyst at the anode, releasing two electrons, and at the cathode, the oxidant (air) is reduced in the presence of hydrogen ions conducted through the Nafion membrane, subsequently forming H₂O as the sole reaction product. The electron release and subsequent oxidation process typically generate a voltage of up to approximately 1.2 V between the fuel electrode and the air electrode under ideal conditions.

[0005] Typically, the catalyst layer comprises a metal-based catalyst, such as transition metals (e.g., platinum, palladium, rhodium, ruthenium, iridium, and osmium). This metal-based catalyst can be included in an unsupported form (e.g., fine metal powder) or supported on an activated and conductive support. In addition to the support material, the catalyst usually contains other components such as proton exchange polymers to enhance the ion conductivity of the catalyst layer. Furthermore, the catalyst layer needs to have a certain degree of porosity to allow reactant gases to flow into the fuel cell and water to flow out of the electrode.

[0006] Besides the properties of the active catalyst metal, the structure and composition of the catalyst support are extremely important for the activity of fuel cells. One type of catalyst support that has attracted significant attention in various fields is carbonaceous particulate materials, such as carbon black. Carbon black generally refers to certain materials produced by the incomplete combustion of carbon-based materials and is characterized as para-crystalline carbon materials. Suitable carbon blacks include furnace black, acetylene black, superconducting black, and their graphitized forms. Exemplary commercially available carbon blacks include Akzo Nobel Ketjen EC300J, Cabot Vulcan XC72R, and Denka acetylene black. Suitable carbonaceous particulate catalyst support materials should exhibit a high surface area (specific surface area) so that the active material can be placed on it to maximize the reactant / catalyst contact area. At the same time, the catalyst material needs to withstand the conditions present during fuel cell operation while also enabling proton transport through the material. At low catalyst loadings, slow kinetics (mass transfer resistance) become a major factor causing performance loss in PEM fuel cells.

[0007] The properties of carbon black, such as surface area, primary particle size, aggregate size, porosity, and surface polarity, can be altered through various processing steps to better suit intended applications. While graphitization is typically used to reduce surface area and enhance the corrosion resistance of carbon, oxidation treatments can modify the chemical properties of surface functional groups, increasing the porosity and surface area of ​​the treated carbon black. Porous carbonaceous particulate materials have attracted attention for various academic and industrial applications.

[0008] In fuel cell applications, porous carbonaceous particulate catalyst support materials must be sufficiently stable under fuel cell operating conditions. Corrosion conditions and temperature shifts can occur under load and during shutdown / start-up processes, at high electrochemical potentials (voltages). While high BET SSA (Surface Area Sag) of carbonaceous catalyst support materials is generally associated with good fuel cell performance, high surface area also leads to reduced corrosion resistance. Therefore, a trade-off between electrochemical surface area and corrosion resistance of carbonaceous particulate catalyst support materials is often necessary.

[0009] For example, WO 2013 / 045894 describes conductive microporous carbon support materials with good corrosion resistance. EP 3552 261 demonstrates porous carbon catalyst supports with pores in the range of 2 nm to 5 nm and a high total pore volume, although not optimized for corrosion resistance. US 9 017 837 B2 discloses a method for manufacturing high surface area graphitized carbon with a c / 2 less than 0.3500 nm.

[0010] In light of the above, there is a need for corrosion-resistant carbonaceous particulate catalyst support materials that also exhibit good mass transfer properties and enable deposited active catalyst materials to possess a high electrochemically active surface area (ECSA). Ideally, such carbonaceous particulate materials should be conductive, protect the active catalyst material from poisoning, and allow gas and liquid flow through the catalyst support material. Such materials would allow for the manufacture of catalyst compositions for fuel cells and electrolyzers that are highly active and can withstand prolonged operation without significant degradation in activity. Summary of the Invention

[0011] The inventors have surprisingly discovered that by carefully optimizing the physicochemical properties, particularly the size distribution of the pores in carbonaceous particulate materials, excellent catalyst support materials can be provided, characterized by a favorable combination of morphology, pore and aggregate structure, electrical conductivity, and surface properties.

[0012] In particular, optimized catalyst support materials have proven to be especially suitable for loading catalysts for hydrogen oxidation reactions, thus producing fuel cell catalysts with a unique and advantageous combination: low corrosion under electrochemical conditions and high catalyst performance as determined by the electrochemical surface area (ECSA) of the catalyst material supported on the carbonaceous particulate material of the present invention, as well as improved mass transfer properties of the catalyst material.

[0013] Therefore, in a first aspect, the present invention relates to carbonaceous particulate materials, wherein the carbonaceous particulate material is characterized by having a particle size of approximately 300 μm. 2 / g to approximately 600 m 2 / g of BET SSA, up to approximately 10 m 2 The micropore area is approximately 60 m² / g, and the pore size range is approximately 5-30 nm. 2 / g to approximately 240 m 2 / g pore area.

[0014] In a second aspect, the present invention relates to a catalyst composition comprising the carbonaceous particulate material and at least one transition metal, or an alloy comprising the at least one transition metal, or a mixture comprising the at least one transition metal.

[0015] Furthermore, in a third aspect, the present invention discloses a catalyst layer comprising the carbonaceous particulate material according to the first aspect of the present invention as described above and / or the catalyst composition according to the second aspect.

[0016] In a fourth aspect, the present invention also relates to a fuel cell or electrolyzer that includes the catalyst layer of the third aspect of the present invention.

[0017] Finally, in a fifth aspect, the present invention provides a method for producing carbonaceous particulate material according to the invention, comprising: forming a material having a particle size of approximately 600 μm... 2 / g and approximately 1500 m 2 High-BET SSA carbonaceous particulate materials with a BET SSA ratio between / g were subjected to inert process gas at temperatures between approximately 900°C and approximately 2200°C and pressures between atmospheric pressure and approximately 80 bar for approximately 10 minutes to up to approximately 600 minutes.

[0018] This high-BET SSA material (600 m) 2 / g to approximately 1500 m 2 / g) can optionally be synthesized in the previous steps, including making a sample with about 5 m 2 / g to approximately 700 m 2 Low-BET SSA carbonaceous particulate material with a BET SSA content of / g is subjected to reactive process gases, which can oxidize at least a portion of the carbon components on the outer surface at a temperature of about 900°C to about 2200°C and a pressure of about 80 bar at atmospheric pressure for about 10 minutes to up to about 600 minutes. Attached Figure Description

[0019] This disclosure will be more readily understood when considered in conjunction with the accompanying drawings and by referring to the following detailed description: Figure 1 The pore volume (in cm³) of the material is shown for certain examples of the invention (IE) and comparative examples (CE). 3 The relationship between the pore size distribution (in grams) and the average pore size. Detailed Implementation

[0020] The inventors have unexpectedly discovered that optimization of the Braun-Emmett-Teller specific surface area (BET SSA) and pore size distribution results in a carbonaceous particulate material with excellent catalyst support properties, making it particularly suitable as a catalyst support in electrochemical applications such as fuel cells, where a combination of high electrochemical surface area and good corrosion resistance and mass transfer properties is desirable. In particular, the inventors have found that the micropore area of ​​the carbonaceous particulate material should be minimized to achieve the advantageous properties reported herein. The combination of the properties of this invention produces the desired properties of downstream catalyst products, such as corrosion resistance and electrochemical surface area (ECSA). These properties make the carbonaceous particulate material according to the invention particularly advantageous for application in gas diffusion layers (GDLs) for fuel cells.

[0021] Those skilled in the art will understand that carbonaceous particulate materials with low (lower) surface areas (especially BET SSA) are characterized by generally exhibiting high (higher) corrosion resistance, but also exhibiting low (lower) distribution area for any transition metal catalyst, resulting in a potential loss of electrochemically active surface area (ECSA). Conversely, carbon supports with high BET SSA enable carbonaceous particulate materials to have good transition metal catalyst distribution, although this typically sacrifices some corrosion resistance of the catalyst support.

[0022] Therefore, the carbonaceous particulate material of the present invention exhibits, in particular, a moderate BET SSA, an increased portion of pores in the 5-30 nm size range, and a reduced portion of pores (micropores) in the < 2 nm size range. Furthermore, downstream products incorporating the carbonaceous material according to the present invention for electrochemical applications (such as gas diffusion layers (GDL) or gas diffusion electrodes (GDE)) are characterized by a good electrochemical surface area (ECSA) and improved mass transfer properties, while maintaining good corrosion resistance during fuel cell operation.

[0023] The carbonaceous particulate materials and downstream products disclosed herein

[0024] As described above, the present invention relates in a first aspect to a carbonaceous particulate material, wherein the carbonaceous particulate material is characterized by having a particle size of approximately 300 μm. 2 / g to approximately 600 m 2 / g of BET SSA, up to approximately 10 m 2 The micropore area is approximately 60 m² / g and the pore size range is approximately 5–30 nm. 2 / g to approximately 240 m 2 / g pore area.

[0025] Therefore, among other parameters, carbonaceous particulate materials are characterized by their corresponding Braun-Emmett-Teller specific surface area (BET SSA). A higher BET SSA for carbon black particles is generally associated with increased surface energy and a larger surface area for interaction between the particle surface and contact media such as gases, byproducts, or catalyst particles. Consequently, a higher BET SSA is also associated with increased corrosion under hydrogen fuel cell operating conditions. Therefore, it is generally understood that the BET SSA of carbon black particles will have a profound impact on the performance of the resulting fuel cell. Typically, carbonaceous particulate materials are characterized by a surface area of ​​approximately 300 μm. 2 / g to approximately 600 m 2 / g BET SSA, however, in some embodiments, the carbonaceous particulate material may also be characterized by approximately 300 m 2 / g to approximately 500 m 2 / g BET SSA, optionally wherein the carbonaceous particulate material is characterized by approximately 310 m 2 / g to approximately 480 m 2 / g or approximately 315 m 2 / g to approximately 460 m 2 / g of BET SSA.

[0026] The inventors have discovered that, for fuel cell applications, catalyst support materials do not significantly benefit from the high surface area attributed to micropores, which still contributes to increased corrosion properties. Therefore, the carbonaceous particulate material according to the invention is characterized by a surface area of ​​at most about 10 μm. 2 / g micropore area. In other embodiments, the carbonaceous particulate material of this aspect of the invention may also be characterized by a micropore area of ​​up to about 9 μm. 2 / g, or at most about 8 mg 2 / g, or at most about 7 m 2 / g, or at most about 6 mg 2 / g, or at most about 5 mg 2 / g micropore area. In some embodiments, the carbonaceous particulate material contains little or no pores with a relatively small number of pores with a diameter of < 2 nm, as determined by conventional methods known to those skilled in the art and including measurements attributable to the surface area of ​​pores with a diameter of less than 2 nm, which are also described in the Measurement Methods section below.

[0027] In contrast, the inventors have discovered that catalyst support materials with an increased pore number in the range of 5 nm to 30 nm result in improved catalyst materials while minimizing carbon corrosion during operation, thus enabling improved fuel cells. Therefore, the carbonaceous particulate catalyst support material according to the invention is characterized by a pore size ranging from approximately 60 nm in the range of 5 nm to 30 nm.2 / g to approximately 240 m 2 / g pore area. In some embodiments, the carbonaceous particulate material may also be characterized by approximately 70 μm pore area in the 5-30 nm pore size range. 2 / g to approximately 220 m 2 / g, or approximately 80 m 2 / g to approximately 200 m 2 / g, or approximately 90 m 2 / g to approximately 180 m 2 The inventors have discovered that carbonaceous particulate materials with high pore areas within this specific pore size range are particularly suitable for the intended purpose. In other embodiments, the carbonaceous particulate materials exhibit at least about 70 μm pore areas in the 5-30 nm pore size range. 2 / g pore area. Optionally, the carbonaceous particulate materials in these embodiments may also exhibit at least 80 m² pore area. 2 / g, or at least about 90 m 2 / g, or at least about 100 m 2 / g pore area.

[0028] In a particular embodiment, the carbonaceous particulate material is characterized by a particle size of approximately 300 μm. 2 / g to approximately 500 m 2 / g of BETSSA, up to about 3% of the micropore area of ​​BET SSA, and about 20% to about 40% of the pore area of ​​BETSSA in the pore size range of 5-30 nm.

[0029] In some embodiments, the carbonaceous particulate material described herein is further characterized in that the micropore area is at most about 3% of the BET SSA. Optionally, in some embodiments, the micropore area is at most about 2.5%, at most about 2%, at most about 1.8%, or at most about 1.5% of the BET SSA.

[0030] Alternatively or additionally, in some embodiments, the carbonaceous particulate material of the present invention is characterized by a pore area of ​​about 20% to about 40% of the BET SSA in the pore size range of 5-30 nm. Optionally, the pore area in the pore size range of 5-30 nm is in some cases about 25% to about 40%, or about 20% to about 35%, or about 25% to about 35% of the BET SSA.

[0031] Carbonaceous particulate materials with a significant portion of pore surface area in the diameter range of less than about 2 nm are generally not considered optimal for achieving the desired properties. Without wishing to be limited by theory, micropores in the diameter range of less than about 2 nm are generally insufficient to protect catalyst materials.

[0032] Carbonaceous particulate materials with pores in the diameter range of 5 nm to 30 nm occupying a significant portion of the pore area are preferred, not least, because it is undesirable to be bound by theory. Such pores are generally suitable for accommodating catalyst particles while still ensuring catalytic activity. The inventors have also unexpectedly discovered that the pores within the carbonaceous particulate materials should preferably not be arbitrarily large, but ideally within a narrow, specific mesopore size range of 5 nm to 30 nm in diameter, because such carbonaceous particulate materials provide the catalyst with the optimal effective surface area and allow for smooth mass transfer. Such materials also offer the possibility of protecting the catalyst from ionomer poisoning.

[0033] Carbon black consists of small, interconnected aggregates of primary particles, and in the context of this document, "inter-aggregate pore size" refers to a measurement of the void space existing between the primary aggregates formed by these particles. In some embodiments, the carbonaceous particulate material is further characterized by an aggregate pore size of about 28 nm to about 46 nm, or about 30 nm to about 44 nm.

[0034] "Total free surface energy" refers to the sum of all energy associated with the exposed surface of a carbonaceous particulate material and allows a person skilled in the art to predict, for example, the material's wetting behavior or its interaction with surrounding media such as gases and / or liquids. Alternatively or additionally, in some embodiments, the total surface free energy of the carbonaceous particulate material may range from about 15 mN / m to about 35 mN / m. Optionally, the total surface free energy may, in some cases, range from about 16 mN / m to about 34 mN / m, or from about 17 mN / m to about 33 mN / m, or from about 18 mN / m to about 32 mN / m.

[0035] The carbonaceous particulate material of the present invention is preferably characterized by high electrical conductivity, which is related to the density of the carbonaceous particulate material being 0.6 g / cm³. 3 The following is Ω The resistivity of a material, as measured by a specific resistivity meter (cm), is inversely proportional to its specific resistivity. In some embodiments, the carbonaceous particulate material can be further characterized as having a specific resistivity of 0.6 g / cm. 3 At a density of at most approximately 0.1 Ω cm, optionally up to approximately 0.08 Ω cm, or at most about 0.07 Ω The specific resistance is cm.

[0036] As described above, one advantage of the present invention is that it provides a carbonaceous particulate material with good corrosion resistance and at least moderate BET SSA. In some embodiments, the carbonaceous particulate material is further characterized in that, after 2 hours of exposure to corrosive conditions, the carbon loss is less than about 2 wt% based on the total weight of the carbonaceous particulate material (as described below in the Measurement Methods section). Optionally, in some embodiments, after 2 hours of exposure to said corrosive conditions, the carbon loss is less than about 1.9 wt%, or less than about 1.85 wt%, based on the total weight of said carbonaceous particulate material.

[0037] When discussing carbon black materials, Raman I... G / I D The ratio is related to the degree of graphitization of the material, and it is understood as the sp content within amorphous carbon particles. 2 The relative amount of hybrid carbon. In some embodiments, the Raman spectroscopy of the carbonaceous particulate material... G / I D The ratio can be at least about 0.80, or at least about 0.90, or at least about 1.00. In other embodiments, the Raman spectroscopy of the carbonaceous particulate material... G / I D The value is approximately 0.80 to approximately 1.40, or approximately 0.90 to approximately 1.30, or approximately 1.00 to approximately 1.20.

[0038] Alternatively or additionally, in some embodiments, the carbonaceous particulate material is characterized by a crystallinity c / 2 value (measured by XRD) of about 0.350 nm to about 0.375 nm. Therefore, the c / 2 value describes the crystallinity in some key spectra. 2 - The average distance between graphite flakes found in the hybridized region, which may be contained within the carbonaceous particulate material. Optionally, the carbonaceous particulate material may be characterized in other embodiments by a c / 2 value of about 0.355 nm to about 0.370 nm, or a c / 2 value of about 0.356 nm to about 0.365 nm.

[0039] The carbonaceous particulate material according to the invention exhibits an optimized aggregate structure, indicated by a high oil absorption value (OAN). The specified OAN provides valuable information about the material's aggregate structure, porosity, surface area, and adsorption properties. The carbon black catalyst support material with the optimized aggregate structure allows liquids (such as water) and gases to flow through the carbonaceous particulate material and allows for good mass transfer characteristics. The water management characteristics of the carbonaceous particulate material according to the invention are particularly advantageous in fuel cell applications, where they have a significant impact on fuel cell efficiency and long-term durability, as both fuel cell overflow and dehydration must be avoided. Furthermore, this optimized aggregate structure of the carbonaceous particulate material according to the invention also provides high electronic conductivity and transport through electrodes in electrochemical applications.

[0040] Therefore, in some embodiments, the carbonaceous particulate material is further characterized by having an oil absorption value (OAN) of about 20 mL / 100 g to about 400 mL / 100 g. In other embodiments, the carbonaceous particulate material has an OAN of about 220 mL / 100 g to about 380 mL / 100 g, or about 240 mL / 100 g to about 340 mL / 100 g, or about 260 mL / 100 g to about 320 mL / 100 g, or about 280 mL / 100 g to about 300 mL / 100 g.

[0041] In other embodiments, the carbonaceous particulate material is further characterized by being approximately 0.4 cm in size. 3 / g to approximately 1.6 cm 3 / g total pore volume. This carbonaceous particulate material may optionally be characterized by approximately 0.5 cm². 3 / g to approximately 1.5 cm 3 / g, or approximately 0.6cm 3 / g to approximately 1.4 cm 3 / g, approximately 0.7 cm 3 / g to approximately 1.3 cm 3 / g total pore volume.

[0042] In a particular embodiment, the carbonaceous particulate material is characterized by a particle size of approximately 300 μm. 2 / g to approximately 600 m 2 / g BETSSA, up to about 10 mg 2 The micropore area is approximately 60 m² / g, within the pore size range of 5-30 nm. 2 / g to approximately 240 m 2 The pore area is approximately 0.7 cm² / g. 3 / g to approximately 1.3 cm 3 / g total pore volume.

[0043] In some embodiments, the carbonaceous particulate material may be further characterized by being approximately 1.2 cm thick. 3 / g to approximately 1.9g / cm 3 The density of xylene, optionally wherein these carbonaceous particulate materials are characterized by a density of approximately 1.25 cm. 3 / g to approximately 1.90 g / cm³ 3 or about 1.3 cm 3 / g to approximately 1.90 g / cm³ 3 or approximately 1.35 cm 3 / g to approximately 1.90 g / cm³ 3 The density of xylene.

[0044] Alternatively or additionally, carbonaceous particulate materials may be characterized by good mass transfer properties in the sense of ionic conductivity throughout the electrode. As those skilled in the art will understand, a high oil absorbance value (OAN) will indicate good mass transfer properties.

[0045] In some embodiments, the carbonaceous particulate material may be carbon black. Suitable carbon black preferably includes, but is not limited to, carbon black selected from the group consisting of: thermal black, acetylene black, furnace black, Ketjen black, and mixtures thereof.

[0046] Catalyst compositions comprising the carbonaceous particulate material of the present invention

[0047] In another aspect, the present invention relates to a catalyst composition comprising a carbonaceous particulate material according to the invention and at least one transition metal, or an alloy comprising at least one transition metal, or a mixture comprising at least one transition metal.

[0048] In some embodiments of the invention, at least one transition metal, or an alloy containing at least one transition metal, or a mixture containing at least one transition metal, is present in particulate form. These particles are optionally deposited on the surface of carbonaceous particles according to the invention. In some cases, the transition metal particles (or alloys or mixtures of transition metals) deposited on the surface of the carbonaceous particulate material are preferably nanoparticles.

[0049] In some embodiments, the catalyst composition is further characterized by at least about 70 m 2 The electrochemical surface area (ECSA) is [value missing] / g. In some embodiments, the carbonaceous particulate material has at least about 75 m² / g. 2 / g, or at least about 80 m 2 / g, or at least about 100 m 2 / g, or at least about 130 m 2 / g ECSA.

[0050] Furthermore, it has been found that in some embodiments, the catalyst composition according to the invention has at least about 70 m² / g ECSA, and is characterized by a carbon loss of less than about 2 wt% based on the total weight of the carbonaceous particulate material after 2 hours of exposure to the corrosive conditions. In some embodiments, the catalyst composition comprises at least one transition metal, or an alloy comprising at least one transition metal, or a mixture comprising at least one transition metal selected from the group consisting of iridium, nickel, cobalt, iron, chromium, palladium, platinum, rhodium, ruthenium, or alloys thereof, or mixtures thereof. In a preferred embodiment, the at least one transition metal is platinum, or an alloy comprising platinum, or a mixture comprising platinum. In embodiments where the catalyst composition comprises transition metal nanoparticles composed of platinum metal, the diameter of the platinum nanoparticles may preferably be between about 1 nm and about 6 nm, or between about 1 nm and about 5 nm, or between about 1 nm and about 4 nm.

[0051] In some embodiments, the at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal, is present in the catalyst composition at a concentration of up to about 80 wt%, up to 70 wt%, up to 60 wt%, up to about 50 wt%, up to about 45 wt%, up to about 40 wt%, or up to about 35 wt%.

[0052] In certain embodiments of the invention, particularly in which the at least one catalyst composition comprising a transition metal is in particulate form, the transition metal particles being small enough to fit within pores in the 5 nm to 30 nm pore size range and to maintain catalytic activity and be protected from any ionomers.

[0053] In some embodiments of this aspect of the invention, the at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal, is platinum and is in particulate form, such as a platinum particle diameter measured by XRD of about 1 nm to 10 nm. In some of these embodiments, the platinum particle diameter measured by XRD is about 1 nm to 8 nm, or about 1 nm to 6 nm, or about 1 nm to 5 nm, or about 1 nm to 4 nm. Alternatively or additionally, in such embodiments, the platinum particle diameter, as measured by TEM, may optionally be about 1 nm to about 10 nm. In some embodiments, the platinum particle diameter, as measured by TEM, is about 1 nm to about 8 nm, or about 1 nm to about 6 nm, or about 1 nm to about 5 nm, or about 1 nm to about 4 nm.

[0054] Catalyst layer comprising the catalyst composition of the present invention

[0055] In another aspect, the present invention relates to a catalyst layer comprising a catalyst composition comprising a carbonaceous particulate material according to the invention.

[0056] In some embodiments, the catalyst layer is in the form of a planar sheet having a thickness of up to about 20 µm, suitable for electrochemical applications, particularly those where a high surface area is desired, such as, for example, fuel cell applications.

[0057] In some embodiments of this aspect of the invention, the catalyst layer is configured to allow a gas or gas mixture to pass through the catalyst layer at ambient pressure or elevated pressure.

[0058] Additionally or alternatively, the catalyst layer is structured such that a liquid can pass through the catalyst layer, across the planar catalyst layer, or directly through the planar axis of the catalyst layer, optionally wherein the liquid is water.

[0059] In some embodiments, the catalyst layer as described herein is stable, conductive, permeable, and catalytically active. Optionally, the catalyst layer is stable, conductive, permeable, and catalytically active under elevated temperatures and / or pressures. In some cases, the elevated temperature of the catalyst layer may refer to a temperature up to about 80°C. In other cases, the elevated temperature refers to a temperature up to about 90°C, or about 100°C, or about 110°C, or up to about 120°C, or up to about 130°C. In some cases, the elevated pressure of the catalyst layer may refer to a pressure up to about 2.0 bar, optionally up to about 2.5 bar, or up to about 3.0 bar, or up to about 3.5 bar, or up to about 4.0 bar, or up to about 4.5 bar, or up to about 5.0 bar.

[0060] When the catalyst layer contains Pt nanoparticles, the catalyst layer can typically contain particles with a content of approximately 100 μg (Pt) / cm³. 2 Approximately 1000 μg (Pt) / cm 2 The loading amount of the Pt nanoparticles, In some embodiments, the catalyst layer according to the invention may further comprise an ion-conducting polymer, optionally wherein the ion-conducting polymer is capable of conducting protons. In some embodiments, the proton-conducting polymer is contained in the catalyst layer in particulate form.

[0061] Fuel cells or electrolyzers comprising carbonaceous particulate materials according to the present invention

[0062] Another related aspect of the invention relates to the use of a catalyst layer according to the invention (which comprises a carbonaceous particulate material as described herein) in the production of a fuel cell or an electrolyzer, and to a fuel cell or electrolyzer comprising a catalyst layer according to the invention.

[0063] In some embodiments, fuel cells or electrolyzers fabricated using the catalyst layers described herein do not exhibit significant signs of corrosion as measured by a decrease in catalytic activity during prolonged exposure to oxygen and / or water vapor or liquid water. Thus, significant signs of corrosion are defined as a decrease in catalytic activity of at least 20%, at least 30%, or at least 40%, and prolonged exposure is defined as exposure to oxygen and / or water vapor or liquid water at room temperature and ambient pressure for at least about 20,000 hours.

[0064] Additionally or alternatively, in some embodiments, the fuel cell or electrolyzer may further comprise an ion-conducting polymer. In some embodiments, the ion-conducting polymer is in the form of a sheet or membrane. Further optionally, the conductive polymer membrane may be a proton exchange membrane (PEM). In a preferred embodiment of the invention, the PEM membrane comprises Nafion.

[0065] In some embodiments, the fuel cell or electrolyzer according to the invention may include a catalyst other than a transition metal-based catalyst in the cathode or anode.

[0066] Method for producing the carbonaceous particulate material of the present invention

[0067] Another aspect of the invention relates to a method for producing the carbonaceous particulate material of the present invention as described herein. The method includes, in its most general form, forming a material with a particle size of approximately 600 μm... 2 / g to approximately 1500 m 2 / g of high BET SSA carbonaceous particulate material was subjected to an inert process gas for about 10 minutes to up to about 600 minutes at a temperature of about 900°C to about 2200°C and a pressure of about ambient pressure to about 80 bar.

[0068] In some embodiments, the high-BET SSA carbonaceous particulate material has a particle size of approximately 650 μm. 2 / g to approximately 1200 m 2 / g, or approximately 700 m 2 / g to approximately 1000 m 2 / g of BET SSA.

[0069] In some embodiments, the inert process gas in the method for producing carbonaceous particulate materials may be selected from N2, Ar, or mixtures thereof. Gases or mixtures thereof composed of N2 and / or Ar have been found to be particularly suitable for the purposes of this invention.

[0070] In some embodiments, the temperature in the method of producing carbonaceous particulate material can be from about 900°C to about 1600°C.

[0071] It will be apparent to those skilled in the art that the processing time must be adjusted to be long enough to obtain particles with a moderate range of BET SSA and the desired pore size distribution, as described above in relation to the characteristics of the carbonaceous particulate material of the present invention.

[0072] Additionally or alternatively, the high-BET SSA carbonaceous particle starting material used in the method for producing carbonaceous particulate material according to the invention can be synthesized from a low-BET SSA carbonaceous particulate material, optionally wherein the low-BET SSA carbonaceous particulate material is a commercially available carbonaceous particulate material.

[0073] The method for producing high-BET SSA carbonaceous particle raw materials used in the method for producing carbonaceous particles according to the present invention can, in its most general form, include making the particles have a particle size of about 5 m... 2 / g to approximately 600 m 2 The low-BET SSA carbonaceous particulate material with a BET SSA content of / g is subjected to a reactive process gas for approximately 10 minutes to approximately 600 minutes, the reactive process gas being capable of oxidizing at least a portion of the carbon components on the outer surface of the low-BET SSA carbonaceous particulate material under the following conditions. (i) a temperature of about 900°C to about 2200°C; and (ii) Approximately ambient pressure to approximately 80 bar.

[0074] In some embodiments of the method for producing high BET SSA carbonaceous particulate material used in the method for producing carbonaceous particulate material according to the present invention, the low BET SSA carbonaceous particulate material includes an outer surface containing a carbon component, and wherein the BET SSA of the high BET SSA carbonaceous particulate material is higher than that of the low BET SSA carbonaceous particulate material.

[0075] Some embodiments of high-BET SSA carbonaceous particulate materials are characterized by approximately 700 m 2 / g to approximately 1200 m 2 / g of BET SSA and approximately 300 mL / 100 g to approximately 750 mL / 100 g of OAN.

[0076] In some embodiments of the method for producing high-BET SSA carbonaceous particulate material, the high-BET SSA carbonaceous particulate material is used in the method for producing the carbonaceous particulate material of the present invention, wherein the low-BET SSA has a density of approximately 20 μm.2 / g to approximately 600 m 2 / g BET SSA. Optionally, low BET SSA carbonaceous particulate materials may have approximately 60 m 2 / g to approximately 450 m 2 / g BETSSA. In some embodiments, the low-BET SSA carbonaceous particulate material has approximately 40 μm. 2 / g to approximately 500 m 2 / g of BET SSA and approximately 120 mL / 100 g to approximately 400 mL / 100 g of OAN.

[0077] In some preferred embodiments of the method for producing high-BET SSA carbonaceous particulate materials, the high-BET SSA carbonaceous particulate materials are used in the method for producing carbonaceous particulate materials according to the invention, and the reactive process gas is selected from the group consisting of CO2, steam, and mixtures thereof. Reactive process gases comprising CO2 and / or steam, or mixtures thereof, have been found to be particularly suitable for the purposes of the invention.

[0078] It will be apparent to those skilled in the art that the processing time for producing high BET SSA carbonaceous particulate material used in the method of manufacturing carbonaceous particulate material according to the invention depends on the type of reactor and the parameters of the starting material and the process conditions in the reactor, such as pressure and temperature. Generally, the processing time must be adjusted to be long enough to obtain particles with the desired high BET SSA, making them suitable for use in the method of producing carbonaceous particulate material according to the invention.

[0079] In some embodiments, both the high-BET SSA and low-BET SSA carbonaceous particle starting materials can be carbon black. Optionally, the CB particles can be selected from: thermal carbon black, acetylene black, or furnace black, Ketjen black, or mixtures thereof, of different types of amorphous carbon black obtained from the incomplete combustion or thermal decomposition of hydrocarbons. Optionally, the thermal carbon black, acetylene black, or furnace black, Ketjen black, or mixtures thereof suitable for use in this invention can be carbon black obtained from commercial sources, or they can be synthesized from hydrocarbon starting materials.

[0080] Various furnace setups can be used in the method of manufacturing the carbonaceous particulate material according to the present invention. In some embodiments, the furnace is a continuous furnace setup or a batch furnace setup. Additionally or alternatively, the furnace may include a fluidized bed setup. In some embodiments, the furnace may be a rotary kiln or a muffle box furnace.

[0081] In some embodiments, the temperature of the method itself can be from about 900°C to about 2200°C, or from about 1000°C to about 1900°C, or from about 1200°C to about 1600°C. During processing in a continuous furnace or batch furnace, the material to be treated is subjected to an inert gas, such as nitrogen or argon, or a mixture thereof. Furthermore, the post-treatment temperature can be maintained at a pressure between about atmospheric pressure and about 80 bar for about 10 minutes to up to about 600 minutes, or about 30 minutes to up to about 500 minutes, or about 50 minutes to up to about 400 minutes. In some embodiments, the cooling process is carried out via a controlled cooling cycle to a certain temperature (below the post-treatment temperature), followed by a natural cooling cycle.

[0082] In view of the methods of the invention as described herein, another aspect of the invention relates to carbonaceous particulate raw materials as described herein, wherein the carbonaceous particulate starting materials are obtainable by the methods described herein.

[0083] definition

[0084] When used in the context of parameters or values ​​mentioned herein, unless otherwise stated, the term “about” includes a deviation of ±10% from a given value.

[0085] It should be noted that the term "a" or "an" entity refers to one or more of the entities; for example, "carbonaceous particulate material" should be understood to mean one or more carbonaceous particulate materials. Therefore, the terms "a" (or "an"), "one or more", and "at least one" are used interchangeably herein.

[0086] Furthermore, the term “and / or” as used herein should be considered as specifically disclosing each of the two specified features or components having or not having the other. Therefore, the term “and / or” as used in phrases such as “A and / or B” herein is intended to include “A and B”, “A or B”, “A” (alone), and “B” (alone). Similarly, the term “and / or” as used in phrases such as “A, B, and / or C” is intended to include each of the following: A, B, and C; A, B, or C; A or C; A or B; B or C; A and C; A and B; B and C; A (alone); B (alone); and C (alone).

[0087] It should be understood that this article uses the word "including" to describe multiple aspects, and also provides other similar aspects described in terms of "consisting of" and / or "substantially consisting of".

[0088] Units, prefixes, and symbols are represented in their International System of Units (SI) accepted form. Numerical ranges include the numbers that define the range.

[0089] Unless otherwise specified, the percentage (%) values ​​specified herein are by weight.

[0090] The headings provided herein are not intended to limit any aspect of this disclosure, which can be obtained by referring to the specification as a whole. Therefore, the terms directly defined below are defined more fully by reference to the entire specification.

[0091] As used herein, the terms “hydrogen ion” and “proton” are used interchangeably, and both refer to a positively charged hydrogen atom, denoted as H. + .

[0092] Unless otherwise specified, the terms "nanoparticles" or "nanoparticle materials" refer to materials with a particle size of 1 × 10⁻⁶. –9 m and 1 × 10 –7 Particles of any shape and size within the m range.

[0093] In the context of this paper, the term "micropore area" is used to describe the size of pores in carbonaceous particulate materials, referring to pores with a diameter equal to or less than 2 nm.

[0094] Unless otherwise specified, the term "corrosion conditions" refers to a static potential of 1 V to 1.4 V in an electrochemical corrosion cell (e.g., available from Gamry Instruments) in 1 M H₂SO₄ at 80°C. Such conditions result in stable corrosion of carbon-based materials and allow for the measurement of the corrosion resistance of carbonaceous particulate materials.

[0095] Measurement methods

[0096] Suitable methods for determining various properties and parameters of graphite particulate materials and compositions / downstream products containing them are described in more detail below.

[0097] BET specific surface area and micropore area [m] from nitrogen adsorption method 2 / g], 5-30 nm pore area and total pore volume

[0098] This method is based on the recording of absorption isotherms of liquid nitrogen at 77 K in the pressure range p / p0 = 0.01–0.995, where p0 is the saturation pressure. Nitrogen adsorption was performed on ASAP2020 from Micromeritics. The sample was degassed in vacuum at 573 K for at least 8 hours prior to analysis. The monolayer capacity was determined according to the method proposed by Brunauer, Emmet, and Teller (Adsorption of Gases in Multi-molecular Layers, J. Am. Chem. Soc., 1938, 60, 309–319). The specific surface area was then calculated based on the cross-sectional area of ​​nitrogen molecules, the monolayer capacity, and the weight of the sample. Microporosity was obtained from t-curves (Harkins & Jura) according to the formula proposed by Harkins and Jura, where the thickness t-value was in the range of 3.5–5 Angström.

[0099]

[0100] Using the method of Barrett, Joyner, and Halenda (BJH), porosity and total pore volume in the range of 5–30 nm were obtained from the adsorption isotherm by thickness curves based on the Halsey equation and corrected by Faas.

[0101] refer to: Ravikovitch, P., Vishnyakov, A., Russo, R., Neinark, A., Langmuir ,16, 2000, 2311-2320, Jagiello, J., Thommes, M., Carbon , 42, 2004, 1227-1232, Barrett, EP, Joyner, LG and Halenda, PP, Journal of the American Chemical Society , 1951, 73, 373-380, Harkins, WD, and Jura, G. J. Chem. Phys. , 1943,11: 430.

[0102] Pore ​​size [nm] within aggregates using mercury porosimetry (mercury porosimetry).

[0103] The pore size within the aggregates was measured using a mercury porosimeter (9600 AutoPore V, from Micromeritics). The sample was inserted into the measurement chamber, and gas was expelled from the sample cell. Mercury was then transferred into the sample cell under vacuum, and pressure was applied to force the mercury into the sample. During the measurement, the applied pressure p and the volume of mercury injected V were recorded. The Washburn equation was applied with a surface tension of 480 mN / m and a mercury contact angle of 130°. From the derivative of the cumulative mercury porosimeter curve, the position of the peak (located in the range of 20–100 nm) was considered to correspond to the size of the pores between particles (within the aggregates).

[0104] Platinum particle size [nm] obtained by transmission electrode microscopy (TEM)

[0105] Platinum particle size was determined by transmission electrode microscopy (TEM). A representative set of calibrated TEM micrographs was analyzed by observing individual particles after image analysis, either manually or computerized.

[0106] Reference: J. Quinson et al. ACS Catal. August 2018 7 , 6627-6635, https: / / doi.org / 10.1021 / acscatal.8b00694

[0107] Interlayer spacing c / 2 [nm] obtained by X-ray diffraction (XRD)

[0108] XRD data were collected using a PANalytical X'Pert PRO diffractometer coupled to a PANalytical X'Celerator detector. The diffractometer has the following characteristics shown in Table 1: Table 1: Instrument Data and Measurement Parameters

[0109] Data was analyzed using PANalytical X' Pert HighScore Plus software.

[0110] The angular position of the maximum peak of the

[002] reflection curve was determined, and the interlayer spacing c / 2 was calculated by applying the Bragg equation (Klug and Alexander, x-ray diffraction procedures, John Wiley & Sons Inc., New York, London (1967)).

[0111] Platinum particle size [nm] obtained by X-ray diffraction (XRD)

[0112] Platinum particle size was determined using X-ray diffraction. Platinum particle size can be obtained by applying the Scherrer formula to selected peaks, as it is inversely proportional to the FWHM (half-maximum width) of a single peak: the narrower the peak, the larger the crystallite size.

[0113] Reference: M. Carmo et al., Journal of Power Sources, 2007. 173 , 860-866.

[0114] Oil absorption value (OAN) [mL / 100 g]

[0115] OAN was measured according to ASTM D2414 (Method A). Paraffin oil was added to the dried carbon black sample in the mixing chamber of the absorber. As the sample absorbed the oil, the viscosity increased. When the viscosity reached a predetermined torque level (400 mNm), the volume of oil added was read. The volume of oil per unit mass of carbon black is OAN.

[0116] Reference: ASTM D2414-01

[0117] Xylene density [g / cm³] 3 ]

[0118] This analysis is based on the principle of liquid exclusion as defined in DIN 51 901. Approximately 2.5 g (accurate to 0.1 mg) of powder is weighed into a 25 ml specific gravity flask. Xylene is added under vacuum (15 Torr). After settling at atmospheric pressure for several hours, the specific gravity flask is conditioned and weighed. Density represents the ratio of mass to volume. Mass is given by the weight of the sample, and volume is calculated from the weight difference between specific gravity flasks filled with the sample powder and those filled with xylene without the sample powder.

[0119] Reference: DIN 51 901

[0120] Total SFE surface free energy [mN / m]

[0121] The total surface free energy was obtained using a tensiometer (K100, Krüss) according to the Washburn method. 1 g of carbon powder was packed into a glass tube and compressed (with a 1 kg preload) for 30 seconds, after which it was brought into contact with different test liquids. The liquids were drawn out due to capillary action. The first test was performed with 50 mL of 99% pure n-hexane, the second with 50 mL of pure water (MilliQ grade), and the third with 50 mL of 99% pure diiodomethane (CH2I2). The surface free energy (SFE) (in mN / m) was calculated using advanced software equipped with the tensiometer from the results of the three measurements.

[0122] I through Raman spectroscopy G / I D Ratio ("R-value")

[0123] Raman analysis was performed at room temperature using a LabRAM-ARAMIS miniature Raman spectrometer from HORIBA Scientific with a 473 nm laser.

[0124] I G / I D The ratio (“R-value”) is based on the so-called ratio of the intensity of the D and G bands. These peaks are located at 1350 cm⁻¹. -1 and 1580 cm -1 The measurements were taken at a specific location, and these peaks are characteristic of carbon materials.

[0125] Specific resistance [Ω] cm]

[0126] 0.5 g of graphite particles were compressed within an insulating mold (a ring made of glass fiber reinforced polymer with an inner diameter of 11.3 mm, inserted into a larger ring made of steel for additional mechanical support) between two charged pistons made of brass (diameter: 1.13 cm). The applied force was controlled during the experiment, while a length gauge was used to measure the relative position of the pistons within the mold (i.e., the height of the powder sample). The pistons were used as electrodes, with a force starting from 0 kN / cm. 2 Up to 20kN / cm 2 Under different pressures, the voltage drop across the sample was measured in situ at a known constant current of 105 mA (2-point resistance measurement).

[0127] The sample resistance was calculated using Ohm's law, assuming that the contact resistance between the piston and the sample was negligible (the calculated resistance was entirely attributable to the sample). The sample resistivity was calculated using the nominal inner diameter of the mold (1.13 cm) and the measured sample height, and expressed in Ω. cm represents the density of the polymer ring. During the experiment, the polymer ring underwent elastic deformation due to lateral expansion (transverse strain) of the sample, but this can be ignored for comparative purposes. A sample with a density of 0.6 g / cm³ was used. 3 The specific resistance (Ω) (cm) was used as the comparison point for the carbon sample.

[0128] refer to: Probst, Carbon, 2002, 40 , 201-205 Grivei, KGK, Kautschuk Gummi Kunststoffe, 2003, 56 , Nr. 9 Spahr, Journal of Power Sources, 2011, 196 3404-3413

[0129] By cyclic voltammetry (CV) (ECSA, m 2 Electrochemical surface area (g) - ECSA-CV method

[0130] Measurement of double-layer capacitance (C) by cyclic voltammetry (CV) dl The electrochemical surface area (ECSA) was estimated. CV was performed at ambient temperature on a VMP3 multichannel potentiostat / galvanostat electrochemical workstation with three electrodes. A reversible hydrogen electrode (RHE) and a graphite electrode were used as the reference and counter electrodes, respectively. A gas diffusion layer (GDL) disk coated with a catalyst film was prepared according to Example 3. A 16 mm catalyst-containing disk was placed in a sample holder and used as the working electrode. The ECSA was estimated according to the following equation:

[0131] The CV curves in the non-Radical region (0 - 0.8 V) are plotted as a function of various scan rates (20, 30, 50, 75, 100, 250, 500, 750, and 1000 mV / s). Then, based on the current density difference (Δj / 2 = (j...) in the middle of the potential window of the CV curve... a -j c / 2)) is used to estimate the double-layer capacitance (C) by the slope of the linear regression between the two layers and the scan rate. dl C s The specific capacitance per unit surface area represents that of the standard electrode material. Here, the C1 of the Pt / C electrode material in 1M H2SO4 solution is based on literature reports. s The value, calculated using ECSA, is 7 x 10. -6 F / cm 2 ECSA is divided from its area in cm² by the mass loading of the catalyst. 2 Convert to m 2 / g. This ECSA-CV method applies to all ECSA references in this paper.

[0132] refer to

[0133] J. Am. Chem. Soc. 2013, 135, 16977-16987

[0134] Chem. Electro. Chem. 2019, 6 (17), 4411-4417

[0135] Z. Phys. Chem. 2020, 234 (5), 979-994

[0136] Benchmark method for carbon corrosion

[0137] Carbon corrosion [%]

[0138] Carbon corrosion was measured on carbon black deposited on a gas diffusion layer (GDL). Samples were measured by preparing a dispersion of the carbon particles of interest and coating it onto carbon paper. A base dispersion containing the carbon black of interest, a wetting agent, a thickener, and a pH adjuster was ultrasonically mixed for 5 minutes. A PTFE binder was added along with rheological additives and surfactants to obtain the final carbon dispersion. The dispersion was coated onto carbon paper, dried at 80°C for 1 hour, and then heated at 380°C for 30 minutes. The resulting film containing the carbonaceous particulate material was cut and then used as the working electrode. The carbon loading range was 0.2–5 mg / cm³. 2 .

[0139] Carbon corrosion rates were measured by chronoamperometry in 1 M H₂SO₄ at 80°C in an electrochemical MultiPort™ corrosion cell from Gamry Instruments. Corrosion currents were measured over periods ranging from 2 h to 24 h during a constant potential holding period of 1 V to 1.4 V. Cyclic voltammetry was also performed at the beginning and end of the test. The wt% of carbon corroded after 2 h was calculated as described in the references.

[0140] Reference: SCBall et al., Journal of Power Sources, 2007. 171(1), 18-25).

[0141] Benchmark methods for gas diffusion electrode (GDE) and oxygen reduction reaction (ORR) activity

[0142] Gas diffusion electrode (GDE) voltammetry and accelerated stress testing (AST)

[0143] A gas diffusion layer (GDL) disk coated with a catalyst film was prepared according to Example 3. A 3 mm catalyst-containing disk was placed in a GDL disk coated with MPL and having a 3 mm hole in the center. A Nafion membrane was placed on top. The entire stack was pressed together using a tablet press (pressure range: 0-15 t) at a pressure of two tons for a duration of 10 min. The gas diffusion layer was then placed in the gas flow field of the lower cell body, followed by the stack containing the 3 mm catalyst disk and the Nafion membrane. Finally, the upper cell body was placed on top of the Nafion membrane. The two body parts were fixed in position by clamps. The compartment of the upper cell body was filled with 15 mL of 4 M perchloric acid or sulfuric acid. Finally, a reversible hydrogen electrode (RHE) was placed in the electrolyte as the reference electrode (RE) and counter electrode (CE, Pt wire).

[0144] All electrochemical measurements were performed at 30°C using a computer-controlled potentiostat and GDE-setting, as reported in Example 4. The analytical procedure for electrochemical analysis of the Pt / C catalyst layer was the same for all catalysts and included the following steps: First, the GDE was removed from the back side (via GDL) with argon or nitrogen. This was done by cleaning the catalyst by cycling at potentials between 0.05 V and 1.10 V relative to the reversible hydrogen electrode (RHE) at a scan rate of 0.2 V / s until a stable cyclic voltammetry (CV) could be observed. (50 cycles). Then, CO stripping measurements and oxygen reduction reaction (ORR) activity measurements were performed. To summarize the study, a second CO stripping measurement was performed. Throughout the experiment, a bubbler was used to humidify the gas and the membrane. During the entire measurement period, the solution resistance was measured by superimposing AC signals with an amplitude of 5 kHz and 5 mV.

[0145] Electrochemical Surface Area (ECSA) - CO Stripping Method

[0146] CO stripping measurements were performed to determine ECSA. Essentially, the catalyst layer was covered with CO gas, which was adsorbed onto the Pt surface. The catalyst was then purged with Ar to remove excess CO. As a next step, CV (scan rate: 50 mV / s) was recorded, derived from the oxidation current of CO to CO2. Finally, multiple CVs were performed under an Ar atmosphere until the Ar background was recovered.

[0147] To determine the electrochemically active surface area (ECSA) of the catalyst under study, the oxidation charge obtained from CO monolayer stripping experiments was analyzed. Briefly, the electrode was held in a CO-saturated electrolyte at 0.05 V relative to the reactive oxygen species (RHE) for 2 minutes. Subsequently, the electrolyte was saturated with Ar (approximately 10 minutes) to remove CO from the electrolyte. The potential was scanned from 0.05 V to 1.10 V relative to the RHE at a scan rate of 50 mV / s to oxidize the adsorbed CO monolayer to CO2. The resulting oxidation charge (QCO) after background subtraction was then compared with the oxidation charge of the monolayer (400 µC / cm²). 2 ECSA is calculated from the ratio of (Pt) and finally normalized to the mass of Pt (mPt).

[0148]

[0149] Oxygen reduction reaction (ORR) activity

[0150] ORR data were analyzed from background-corrected polarization curves. Background polarization curves were recorded in an Ar-purged electrolyte. ORR activity was then evaluated by a forward scan at 0.90 V relative to RHE. Mass activity (MA) was obtained by normalizing the activity with Pt mass. Specific activity (SA) was determined by measuring the current density (mA / m). 2 (Normalized to ECSA to obtain)

[0151] Before ORR activity measurement, oxygen was allowed to flow through the pipeline for 10 minutes. For the last 5 minutes, a potential of 0.80 V relative to the RHE was applied. This ensured that all gas lines were completely filled with oxygen and that the catalyst layer was equally wetted across the entire surface. ORR activity measurement was performed in a potential-controlled mode with a potential range between 1.00 V (relative to RHE) and 0.10 V (relative to RHE). The potential was preset to 1.00 V (relative to RHE) and then decreased in 25 mV steps until 0.10 V (relative to RHE) was reached. At each step, the potential was held constant for 1 minute to reach steady-state conditions. The current measured in the last 10 seconds was averaged for analysis.

[0152] Various aspects of the invention have been described in general terms, and it will be apparent to those skilled in the art that many modifications and minor variations may be made without departing from the spirit and scope of the invention. The invention is further described with reference to the following non-limiting embodiments: 1. A carbonaceous particulate material, characterized in that... a) Approximately 300 m 2 / g to approximately 600 m 2 / g of BET SSA; b) At most about 10 m 2 The micropore area per g; and c) Approximately 60 μm in the pore size range of 5 nm - 30 nm. 2 / g to approximately 240 m 2 / g pore area.

[0153] 2. The carbonaceous particulate material according to Embodiment 1, wherein the carbonaceous particulate material is characterized by having a particle size of approximately 300 μm. 2 / g to approximately 500 m 2 / g BET SSA, optionally wherein the carbonaceous particulate material has approximately 310 m 2 / g to approximately 480 m 2 / g, or approximately 315 m 2 / g to approximately 460 m 2 / g of BET SSA.

[0154] 3. The carbonaceous particulate material according to Embodiment 1 or Embodiment 2, wherein the carbonaceous particulate material has a particle size of at most about 9 μm. 2 / g, or at most about 8 mg 2 / g, or at most about 7 m 2 / g, or at most about 6 mg 2 / g, or at most about 5 mg 2 / g micropore area.

[0155] 4. The carbonaceous particulate material according to any one of embodiments 1-3, wherein the pore area in the pore size range of 5-30 nm is approximately 70 m². 2 / g to approximately 220 m 2 / g or approximately 80 m 2 / g to approximately 200 m 2 / g, or approximately 90 m 2 / g to approximately 180 m 2 / g.

[0156] 5. The carbonaceous particulate material according to any one of embodiments 1-4, wherein the micropore area accounts for up to about 3% of the BET SSA, optionally wherein the micropore area accounts for up to about 2.5%, up to about 2%, up to about 1.8% or up to about 1.5% of the BET SSA.

[0157] 6. The carbonaceous particulate material according to any one of embodiments 1-5, wherein the pore area in the 5-30 nm pore range accounts for about 20% to about 40% of the BET SSA, optionally wherein the pore area in the 5-30 nm pore range accounts for about 25% to about 40%, or about 20% to about 35%, or about 25% to about 35% of the BET SSA.

[0158] 7. A carbonaceous particulate material according to any one of embodiments 1-6, wherein the carbonaceous particulate material is further characterized by a c / 2 value of about 0.350 nm to about 0.375 nm, optionally about 0.355 nm to about 0.370 nm, or about 0.356 nm to about 0.365 nm as measured by XRD.

[0159] 8. The carbonaceous particulate material according to any one of embodiments 1-7, wherein the carbonaceous particulate material is further characterized by an oil absorption value (OAN) of about 200 mL / 100 g to about 400 mL / 100 g, optionally wherein the particulate carbon has an OAN of about 240 mL / 100 g to about 340 mL / 100 g, or wherein the particulate carbon has an OAN of about 280 mL / 100 g to about 300 mL / 100 g.

[0160] 9. A carbonaceous particulate material according to any one of embodiments 1-8, wherein the carbonaceous particulate material is further characterized by a Raman spectral density of at least about 0.80, or at least about 0.90, or at least about 1.00. G / I D Value; optionally, among which Raman I G / I D The values ​​are approximately 0.80 to approximately 1.40, or approximately 0.90 to approximately 1.30, or approximately 1.00 to approximately 1.20.

[0161] 10. The carbonaceous particulate material according to any one of embodiments 1-9, wherein the carbonaceous particulate material is further characterized in that after being exposed to corrosive conditions for 2 hours, the carbon loss is less than 2 wt% based on the total weight of the carbonaceous particulate material, optionally wherein, after being exposed to corrosive conditions for 2 hours, the carbon loss is less than 1.9 wt% or less than 1.85 wt% based on the total weight of the carbonaceous particulate material.

[0162] 11. A carbonaceous particulate material according to any one of embodiments 1-10, wherein the carbonaceous particulate material is a carbon black, optionally wherein the carbon black is selected from thermal black, acetylene black, furnace black, and Ketjen black.

[0163] 12. A catalyst composition comprising a carbonaceous particulate material of any one of embodiments 1-11 and at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal.

[0164] 13. The catalyst composition according to embodiment 12, wherein the at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal, is in particulate form, optionally wherein the at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal, is in nanoparticle form and deposited on the surface of the carbonaceous particulate material.

[0165] 14. The catalyst composition according to Embodiment 12 or Embodiment 13, wherein the at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal is iridium, nickel, cobalt, iron, chromium, palladium, platinum, rhodium and / or ruthenium, optionally wherein the at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal is platinum.

[0166] 15. The catalyst composition according to any one of embodiments 12-14, wherein the at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal accounts for at most about 80 wt%, or at most about 70 wt%, or at most about 60 wt%, or at most about 50 wt%, or at most about 45 wt%, or at most about 40 wt%, or at most about 35 wt% of the catalyst composition.

[0167] 16. The catalyst composition according to any one of embodiments 12-15, wherein the catalyst composition is further characterized by having at least about 70 m 2 The electrochemical surface area (ECSA) is 1 / g, optionally wherein the carbonaceous particulate material has at least about 75 m² / g. 2 / g, or at least about 80 m 2 / g, or at least about 100 m 2 / g, or at least about 130 m 2 / g ECSA, as measured using the ECSA-CV method described herein.

[0168] 17. A catalyst layer comprising a carbonaceous particulate material according to any one of embodiments 1-11 and / or a catalyst composition according to any one of embodiments 12-16.

[0169] 18. A fuel cell or electrolyzer comprising a carbonaceous particulate material according to any one of embodiments 1-11, a catalyst composition according to any one of embodiments 12-16, and / or a catalyst layer according to embodiment 17.

[0170] 19. A method for producing carbonaceous particulate material as defined in any one of embodiments 1-11, comprising: making a material having a particle size of about 600 μm2 / g and approximately 1500 m 2 High-BET SSA carbonaceous particulate materials with BET SSA between / g undergo: a) Inert process gas; b) At a temperature of approximately 900°C to approximately 2200°C; c) Under pressures ranging from atmospheric pressure to approximately 80 bar; and d) Lasts approximately 10 minutes to approximately 600 minutes.

[0171] 20. The method according to embodiment 19, wherein the inert process gas is selected from the group consisting of N2, Ar, and mixtures thereof, optionally wherein the inert process gas consists of N2, Ar, and mixtures thereof.

[0172] 21. The method according to embodiment 19 or embodiment 20, wherein the temperature is between 900°C and about 1600°C.

[0173] 22. The method according to any one of embodiments 19-21, wherein the high-BET SSA carbonaceous particle starting material has a particle size of approximately 650 μm. 2 / g to 1200 m 2 / g of BET SSA, Optionally, the high-BET SSA carbonaceous particulate material has a particle size of approximately 700 m. 2 / g to approximately 1000 m 2 / g of BET SSA.

[0174] 23. The method according to any one of embodiments 19-22, wherein the high BET SSA carbonaceous particle starting material is prepared in advance, including making it having a particle size of about 5 μm 2 / g to approximately 700 m 2 / g of low-BET SSA carbonaceous particulate material undergoes: a) A reactive process gas capable of oxidizing at least a portion of the carbon components on an outer surface; b) At a temperature of approximately 900°C to approximately 2200°C; c) At atmospheric pressure to approximately 80 bar; and d) Lasts approximately 10 minutes to approximately 600 minutes.

[0175] 24. The method according to embodiment 23, wherein the reactive process gas is selected from the group consisting of: CO2, water vapor, and mixtures thereof. Optionally, the reactive process gas is selected from the group consisting of: CO2, water vapor, and mixtures thereof.

[0176] 25. The method according to embodiment 23 or embodiment 24, wherein the low-BET SSA carbonaceous particulate material has a particle size of approximately 20 μm. 2 / g to approximately 600 m 2 / g of BET SSA, Optionally, the low-BET SSA carbonaceous particulate material has approximately 60 μm 2 / g to approximately 450 m 2 / g of BET SSA.

[0177] 26. The method according to any one of embodiments 23-25, wherein the low-BET SSA carbonaceous particulate material includes an outer surface containing a carbon component; and

[0178] The BET SSA of high-BET SSA carbonaceous particulate materials is higher than that of low-BET SSA carbonaceous particulate materials.

[0179] 27. The method according to any one of embodiments 23-26, wherein the low-BET SSA carbonaceous particulate material has a particle size of approximately 40 μm. 2 / g to approximately 500 m 2 / g of BET SSA and approximately 120 mL / 100 g to approximately 400 mL / 100 g of OAN.

[0180] 28. The method according to any one of embodiments 19-27, wherein the high-BET SSA carbonaceous particulate material has a particle size of approximately 700 μm. 2 / g to approximately 1200 m 2 / g of BET SSA and approximately 300 mL / 100 g to approximately 750 mL / 100 g of OAN.

[0181] 29. The method according to any one of embodiments 19-28, wherein the carbonaceous particle starting material is a carbon black, optionally wherein the carbonaceous particle raw material is selected from the group consisting of thermal carbon black, acetylene black, furnace black, Ketjen black and mixtures thereof.

[0182] Example

[0183] Example 1 - Preparation of carbonaceous particulate materials

[0184] Various carbonaceous particulate materials according to this disclosure are produced by the methods described herein and compared with a variety of known / commercially available carbon blacks.

[0185] Typically, to synthesize the carbon black material according to the invention, the starting carbon black material is loaded into a fixed fluidized bed or muffle furnace in an intermittent assembly, or continuously fed into a fluidized bed furnace or rotary kiln and subjected to an inert gas such as nitrogen or argon. Temperatures between 900°C and 2200°C are used. The post-treatment temperature is maintained at a pressure between about atmospheric pressure and about 80 bar for 10 to up to 600 minutes. After cooling to room temperature, the carbonaceous particulate material according to the invention is obtained.

[0186] Examples IE1-IE5 of this invention were prepared using high-BET SSA carbonaceous particulate material CE3 as the starting material. The specific synthesis method is as follows: The material from Example IE1 was prepared using a high-temperature muffle furnace. 142 g of the starting material was loaded into an Al₂O₃ crucible and placed in the furnace at room temperature. The furnace was then heated to an operating temperature of 1400°C and held for 360 minutes. After 360 minutes, the sample was cooled to 300°C in a controlled manner, followed by natural cooling. The treatment was carried out under a nitrogen atmosphere at a constant flow rate of 14 L / min.

[0187] The material from Example IE2 was prepared using a high-temperature muffle furnace. 144 g of the starting material was loaded into an Al₂O₃ crucible and placed in the furnace at room temperature. The furnace was then heated to an operating temperature of 1400°C and held for 240 minutes. After 240 minutes, the sample was cooled to 300°C in a controlled manner, followed by natural cooling. The treatment was carried out under a nitrogen atmosphere at a constant flow rate of 14 L / min.

[0188] The material from Example IE3 was prepared using a high-temperature muffle furnace. 222 g of the starting material was loaded into an Al₂O₃ crucible and placed in the furnace at room temperature. The furnace was then heated to an operating temperature of 1400°C and held for 60 min. After 60 min, the sample was cooled to 300°C in a controlled manner, followed by natural cooling. The treatment was carried out under a nitrogen atmosphere at a constant flow rate of 20 L / min.

[0189] The material from Example IE4 was prepared using a high-temperature muffle furnace. 107 g of the starting material was loaded into an Al₂O₃ crucible and placed in the furnace at room temperature. The furnace was then heated to an operating temperature of 1400°C. After reaching 1400°C, the sample was immediately cooled to 300°C in a controlled manner, followed by natural cooling. The process was carried out under a nitrogen atmosphere at a constant flow rate of 20 L / min.

[0190] The material from Example IE5 was prepared using a high-temperature muffle furnace. 103 g of the starting material was loaded into an Al₂O₃ crucible and placed in the furnace at room temperature. The furnace was then heated to an operating temperature of 1400°C. After reaching 1400°C, the sample was immediately cooled to 300°C in a controlled manner, followed by natural cooling. The treatment was carried out under a nitrogen atmosphere at a constant flow rate of 20 L / min.

[0191] The carbonaceous particulate materials (designated IE1-IE5) disclosed herein will also be compared with known commercially available carbon black materials (designated CE1-CE6).

[0192] Table 2a: Physicochemical properties of the carbonaceous particulate materials prepared in Example 1

[0193] Table 2b: Physicochemical properties of the carbonaceous particulate materials prepared in Example 1 (continued)

[0194] Figure 1 The carbonaceous particulate material of the present invention further illustrates the pore size distribution compared to commonly used carbon black. The carbonaceous particulate material according to the present invention demonstrates an increased number of pores in the pore size range of 5 nm to 30 nm compared to the comparative example.

[0195] For applications in fuel cells or electrolyzers, resistivity and resistance to corrosion are two important parameters affecting the quality and lifespan of the resulting product. Therefore, the carbonaceous particulate materials (designated IE1 to IE5) according to this disclosure will also be compared with known and commercially available carbon black materials. The results of the measurements are summarized in Table 3. For convenience, the BETSSA values ​​from Table 2a are also reproduced below: Table 3: Resistivity and carbon corrosion of the carbonaceous particulate material prepared in Example 1 after 2 h.

[0196] As can be seen from Table 3 above, the carbonaceous particulate material according to the present invention allows for a particle size of 300 m. 2 / g to 600 m 2 The consistent low corrosion within / gBET SSA may be due to the low micropore area (< 10 μm). 2 / g) related. The only comparative example with comparable corrosion resistance, CE2, is characterized by very low BET SSA (64 m). 2 Therefore, it cannot provide sufficient surface area for the catalyst material, resulting in low ECSA ( / g).

[0197] As can be seen from Table 3, the examples of the present invention exhibit lower resistivity compared to the comparative examples. This lower resistivity is considered to be associated with a higher structural density as measured by OAN. The lower resistivity will contribute to improved conductivity in the catalyst layer.

[0198] Materials with low BET SSA and high graphitization are typically expected to be characterized by low corrosion. However, the data in Table 3 illustrate the importance of the optimal combination of properties as materials for this invention. CE4 and CE5 have low BET SSA and high graphitization (I G / I D However, it exhibits high corrosiveness.

[0199] Example 2 - Preparation of catalyst materials from carbonaceous particulate materials

[0200] In order to obtain a suitable gas diffusion electrode (GDE) catalyst material, the Pt active catalyst material must be deposited on the carbonaceous particulate material according to the present invention and commercially available carbon black.

[0201] First, a colloidal suspension of Pt nanoparticles was synthesized by mixing a 50 mL, 0.4 M solution of NaOH in ethylene glycol with a 50 mL, 1 g solution of H₂PtCl₆·6H₂O in ethylene glycol under vigorous stirring, resulting in a pale yellow platinum hydroxide or platinum oxide colloidal solution. The reaction was carried out under an inert atmosphere or Ar. The colloidal solution was then heated to 160°C while purging the system with Ar gas for 3 h, yielding a dark brown homogeneous colloidal suspension of metal particles with a Pt concentration of 4 g Pt per liter of ethylene glycol.

[0202] To load Pt nanoparticles onto carbonaceous particulate materials, 30 mL of 1 M HCl was added to 7.3 mL of a colloidal Pt nanoparticle solution for precipitation. The solution was centrifuged (4000 rpm, 6 min) and the supernatant solvent was discarded. This step was repeated, and the Pt nanoparticles were then redispersed in acetone. Finally, the synthesized Pt nanoparticles were deposited onto different carbonaceous particulate materials by mixing these Pt nanoparticle suspensions (in acetone) with carbon black (suspended in 3 mL of acetone and sonicated for 1 h). Finally, the catalyst-loaded carbonaceous particulate materials were dried to obtain a material containing carbon black and 30 wt% platinum.

[0203] Typically, Pt nanoparticles prepared according to the described method will be characterized by diameters ranging from approximately 1 nm to approximately 6 nm. The Pt nanoparticle sizes of catalyst-supported carbonaceous particulate materials were measured using the TEM and XRD methods described herein, and the results are shown in Table 4 below.

[0204] Table 4: Pt Nanoparticle Size Measurement

[0205] Example 3 - Fabrication of a gas diffusion electrode (GDE) containing carbonaceous particulate material

[0206] In order to be used as a catalyst material in a gas diffusion electrode (GDE), a catalyst layer must be prepared from a carbonaceous particulate catalyst composition.

[0207] To prepare the catalyst ink, dried catalyst powder was dispersed in a mixture of Milli-Q water and isopropanol (volume ratio 3:1). The mixture was sonicated at room temperature for 5 minutes to disperse the powder. Subsequently, a Nafion solution was added so that the ink contained a C:Nafion mass ratio of 1. The ink was sonicated again for 5 minutes. For all catalysts, the final ink had a Pt concentration of 0.5 mg / mL.

[0208] Catalyst membranes were prepared by vacuum filtering catalyst ink onto a GDL (Gross Distillation Line). For vacuum filtration, the ink was first diluted with Milli-Q water to a Pt concentration of 0.05 mg / mL (mixture volume ratio 1:3). The ink was then added to a vacuum apparatus and filtered through a GDL coated with MPL. A 3 mm diameter disc was cut from the membrane-coated GDL (diameter = 4 cm) and used as a GDE (Gross Deposition Electrode). All studied GDEs prepared from commercially available Pt / C catalysts exhibited a concentration of 208 μg (Pt) / cm on the GDL. 2 Pt load.

[0209] GDE consists of a semi-fuel cell in which air passes through a gas diffusion layer (GDL) / MPL and reaches a catalyst layer in contact with the electrolyte solution. This system allows for the study of the performance and stability of the surface-active platinum and catalyst layer, as expressed by parameters such as CO-stripping profiles, polarization profiles, and accelerated stress tests.

[0210] Typically, materials according to the present invention, having intermediate BET SSA, low microporosity, and high porosity in the range of 5-30 nm, generally have a porosity greater than 100 μm. 2 / g, and in some cases higher than 130 m 2 ECSA values ​​per g. Conversely, except for Pt-CE3, the comparative examples showed electrochemical surface areas below 90 m². 2 / g. Although Pt-CE3 has a value higher than 100 m 2 / g ECSA, but the CE3 material exhibits increased carbon corrosivity compared to the embodiments of the present invention. The ECSA values ​​of the catalyst-loaded carbonaceous particulate material were measured using the ECSA-CV method described herein, and the results are shown in Table 5 below.

[0211] Table 5 - ECSA Measurements

[0212] To avoid being bound by theory, it is believed that, compared with the comparative example, the surface area range (in the range of 300-600 m²) 2 The optimal combination of low corrosion and high ECSA is due to the optimal combination of pore size distribution and surface properties (between / g).

Claims

1. A carbonaceous particulate material, wherein, The carbonaceous particulate material is characterized in that d) Approximately 300 m 2 / g to approximately 600 m 2 / g of BET SSA; e) At most about 10 m 2 The micropore area per g; and f) Approximately 60 μm in the 5 nm - 30 nm pore size range 2 / g to approximately 240 m 2 / g pore area.

2. The carbonaceous particulate material according to claim 1, wherein, The micropore area accounts for up to about 3% of the BET SSA, optionally including up to about 2.5%, up to about 2%, up to about 1.8%, or up to about 1.5% of the BET SSA.

3. The carbonaceous particulate material according to any one of claims 1-2, wherein, The pore area in the 5-30 nm pore range accounts for about 20% to about 40% of the BET SSA, optionally wherein the pore area in the 5-30 nm pore range accounts for about 25% to about 40%, or about 20% to about 35%, or about 25% to about 35% of the BET SSA.

4. The carbonaceous particulate material according to any one of claims 1-3, wherein, The carbonaceous particulate material is further characterized in that, after exposure to corrosive conditions for 2 hours, the carbon loss is less than 2 wt% based on the total weight of the carbonaceous particulate material, optionally wherein, after exposure to corrosive conditions for 2 hours, the carbon loss is less than 1.9 wt% or less than 1.85 wt% based on the total weight of the carbonaceous particulate material.

5. The carbonaceous particulate material according to any one of claims 1-4, wherein, The carbonaceous particulate material is carbon black, optionally selected from thermal black, acetylene black, furnace black, and Ketjen black.

6. A catalyst composition comprising a carbonaceous particulate material according to any one of claims 1-5 and at least one transition metal, or an alloy comprising the at least one transition metal, or a mixture comprising the at least one transition metal.

7. The catalyst composition according to claim 6, wherein, The at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal, is iridium, nickel, cobalt, iron, chromium, palladium, platinum, rhodium, and / or ruthenium. Optionally, the at least one transition metal, or an alloy containing the at least one transition metal, or a mixture containing the at least one transition metal, is platinum.

8. The catalyst composition according to any one of claims 6-7, wherein, The catalyst composition comprises about 35 wt% to about 80 wt% of the transition metal or the alloy, and the catalyst composition is further characterized by having at least about 70 m 2 Electrochemical surface area (ECSA) of / g, optionally wherein the carbonaceous particulate material has at least about 75 m² / g as measured using the ECSA-CV method described herein. 2 / g, or at least about 80 m 2 / g, or at least about 100 m 2 / g, or at least about 130m 2 / g ECSA.

9. A catalyst layer comprising a carbonaceous particulate material according to any one of claims 1-5, and / or a catalyst composition according to any one of claims 6-8.

10. A fuel cell or electrolyzer comprising a carbonaceous particulate material according to any one of claims 1-5, a catalyst composition according to any one of claims 6-8, and / or a catalyst layer according to claim 9.

11. A method for producing carbonaceous particulate material according to any one of claims 1-5, comprising having a particle size of about 600 m 2 / g and approximately 1500 m 2 High-BET SSA carbonaceous particulate materials with BET SSA between / g undergo: e) Inert process gases; f) At a temperature of approximately 900°C to approximately 2200°C; g) Under atmospheric pressure to approximately 80 bar; and (h) lasts from about 10 minutes to about 600 minutes.

12. The method according to claim 11, wherein, The inert process gas is selected from the group consisting of N2, Ar, and mixtures thereof. Optionally, the inert process gas consists of N2, Ar, and mixtures thereof.

13. The method according to any one of claims 11-12, wherein, Pre-preparation of high-BET SSA carbonaceous particle starting materials, including making them have a particle size of approximately 5 μm 2 / g to approximately 700 m 2 / g of low-BET SSA carbonaceous particulate material undergoes: e) A reactive process gas capable of oxidizing at least a portion of the carbon components on the outer surface; f) At a temperature of approximately 900°C to approximately 2200°C; g) Under atmospheric pressure to approximately 80 bar; and (h) lasts from about 10 minutes to about 600 minutes.

14. The method according to claim 13, wherein, The reactive process gas is selected from the group consisting of CO2, water vapor, and mixtures thereof.

15. The method according to any one of claims 13-14, wherein, The low-BET SSA carbonaceous particulate material includes an outer surface containing a carbon component; and The BET SSA of the high-BET SSA carbonaceous particulate material is higher than that of the low-BET SSA carbonaceous particulate material.

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