Silicate treated carbon black for use in battery applications

Abstract

The present disclosure relates to paste compositions that contain a lead oxide, a carbon black comprising an alkali metal silicate impregnated thereon, a lignin source, barium sulfate, sulfuric acid, and optionally additional water. Electrodes, such as electrode plates, are prepared by first forming the paste composition, and then drying and curing the paste composition onto a metal current collector to form the electrodes. The electrodes can be utilized in lead acid batteries.

Description

SILICATE TREATED CARBON BLACKFOR USE IN BATTERY APPLICATIONS REFERENCE TO RELATED APPLICATION

[0001] This application is being filed on October 22, 2025, as a PCT International Patent Application and claims the benefit of and priority to U.S Patent Application No. 63 / 711,188, filed on October 24, 2024, the disclosure of which is incorporated herein by reference in its entirety.TECHNICAL FIELD

[0002] The present disclosure relates to compositions containing a carbon black comprising an alkali metal silicate impregnated thereon, and more particularly, relates to paste compositions containing the carbon black that can be used to produce electrodes, batteries containing the electrodes, and related methods for making electrodes from paste compositions containing the carbon black.BACKGROUND

[0003] The life cycle of lead acid batteries in many cases is only 2-3 years, whereas a desirable life cycle can reach up to 6 years, but is generally not attainable. Improvements in cold cranking performance also are desired. Thus, it would be beneficial to develop new paste compositions and resulting electrodes that would overcome these deficiencies.Accordingly, it is to these ends that the present invention is generally directed.SUMMARY

[0004] In accordance with the purpose(s) of the invention, as embodied and broadly described herein, this disclosure relates to paste compositions, electrodes, and batteries that utilize carbon blacks that contain an alkali metal silicate impregnated thereon.

[0005] In one aspect, a paste composition (or formulation) is provided, and in this aspect, the composition can comprise (i) a lead oxide, (ii) a carbon black comprising an alkali metal silicate impregnated thereon, (iii) a lignin source, (iv) barium sulfate (BaSCh), and (v) sulfuric acid. Additional (vi) water also can be present in the paste composition.

[0006] In another aspect, an electrode prepared by a process is provided, and in this aspect, the electrode can be prepared by a process comprising (a) contacting (or reacting) in any order (i) a lead oxide, (ii) a carbon black comprising an alkali metal silicate impregnated thereon, (iii) a lignin source, (iv) barium sulfate (BaSO i). and (v) sulfuric acid (and optionally, additional (vi) water), to form a paste composition, and then (b) drying and curing the paste composition onto a metal current collector to form the electrode.

[0007] In yet another aspect, a process for preparing an electrode is provided, and in this aspect, the process can comprise (a) contacting (or reacting) in any order (i) a lead oxide, (ii) a carbon black comprising an alkali metal silicate impregnated thereon, (iii) a lignin source, (iv) barium sulfate (BaSCh), and (v) sulfuric acid (and optionally, additional (vi) water), to form a paste composition, and then (b) drying and curing the paste composition onto a metal current collector to form the electrode.

[0008] Additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.DESCRIPTION

[0009] The present invention can be understood more readily by reference to the following detailed description of the invention and the Examples included therein.

[0010] Before the present compounds, compositions, articles, systems, devices, and / or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, example methods and materials are now described.

[0011] All publications (including ASTM methods) mentioned herein are incorporated herein by reference in their entirety’ to disclose and describe the methods and / or materials in connection with which the publications are cited.

[0012] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, example methods and materials are now described.

[0013] As used herein, unless specifically stated to the contrary’, the singular forms “a,” “an’" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a carbon black" or “a lignin source” includes mixtures of two or more carbon blacks or lignin sources, respectively.

[0014] Various numerical ranges are disclosed herein. When a range of any type is disclosed or claimed, the intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. As a representative example, the present disclosure recites that the weight ratio of the barium sulfate to the carbon black in a paste composition can be in certain ranges. By a disclosure that the weight ratio can be in a range from 10: 1 to 1:10, the intent is to recite that the weight ratio can be any ratio in the range and. for example, can include any range or combination of ranges from 10: 1 to 1:10, such as from 5:1 to 1 :5, from 6: 1 to 2: 1 , or from 6:1 to 3: 1 , and so forth. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0015] As used herein, the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0016] The terms “contacting” and “combining” and the like are used herein to describe compositions, processes, and methods in which the materials or components are contacted combined together in any order, in any manner, and for any length of time, unless otherwise specified. For example, the materials or components can be blended, mixed, slurried, dissolved, reacted, cured, treated, impregnated, compounded, sprayed, or otherwise contacted or combined in some other manner or by any suitable method or technique.

[0017] The terms “paste composition’" and “paste formulation” and the like do not depend upon the actual product or composition resulting from the contact or reaction of the initial components of the disclosed or claimed paste composition / formulation, or the fate of the lead oxide(s), the carbon black(s), the lignin source(s), the barium sulfate, and the sulfuric acid, after combining these components. Therefore, the “paste composition” and “paste formulation” encompass the initial starting components of the composition, as well as whatever product(s) may result from contacting (or reacting) these initial starting components.

[0018] The term “base carbon black"’ means the carbon black onto which the alkali metal silicate is impregnated thereon to form the “carbon black” (the carbon black comprising an alkali metal silicate impregnated thereon). The base carbon black and the carbon black may have the same or different iodine adsorption, oil absorption, nitrogen BET surface area, and other features or properties.

[0019] Disclosed are the components to be used to prepare the compositions of the invention as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A. B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C- E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional stepscan be performed with any specific embodiment or combination of embodiments of the methods of the invention.

[0020] Each of the materials disclosed herein are either commercially available and / or the methods for the production thereof are known to those of skill in the art.

[0021] It is understood that the compositions prepared by the disclosed methods have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.

[0022] Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.A. Paste Compositions

[0023] As briefly described above, paste compositions (also referred to as paste formulations) disclosed herein can comprise (i) a lead oxide, (ii) a carbon black comprising an alkali metal silicate impregnated thereon, (iii) a lignin source, (iv) barium sulfate (BaSCfi), and (v) sulfuric acid. Depending upon a variety of factors, such as the paste weight, the desired viscosity7of the composition or formulation, and requirements for subsequent dry ing and curing, the paste composition can further comprise (vi) water in any suitable amount.

[0024] The paste composition can be formed by contacting (or reacting) the following components in any order: (i) a lead oxide, (ii) a carbon black comprising an alkali metal silicate impregnated thereon, (iii) a lignin source, (iv) barium sulfate (BaSO-i), and (v) sulfuric acid. Optionally, additional (vi) w ater of any suitable amount can be added to any one or a combination of two or more of these components, and in any order or sequence. For example, in one aspect, the carbon black, the lignin source, and the barium sulfate can be combined first, then followed by combining the sulfuric acid (and optional w ater) and the lead oxide to form the paste composition. The pre-blend of the carbon black, the lignin source, and the barium sulfate often is referred to in the art as an expander.

[0025] The lead oxide can be any suitable PbxOy compound, examples of which include PbO, PbCh, PbsCh. Pb2Ch, and the like, as well as any combination thereof.Ordinarily, although not limited thereto, the lead oxide typically utilized in the paste composition is PbO.

[0026] Other ingredients or components also can be included to form the paste composition. Non-limiting examples include a conductive additive (e.g.. graphite and / or graphene), or a tetrabasic lead (e.g., tetrabasic lead sulfate), or both the conductive additive and the tetrabasic lead. Thus, the paste composition can comprise (or can be formed by contacting) the lead oxide, the carbon black, the lignin source, the barium sulfate, the sulfuric acid (and optional water), and the conductive additive (e.g., graphite and / or graphene); alternatively, and the tetrabasic lead (e.g., tetrabasic lead sulfate); or alternatively, and both the conductive additive and the tetrabasic lead.

[0027] The relative amounts of the respective components in the paste composition can vary depending upon the desired properties of the paste composition (and the resulting products formed from the paste composition). Based on the weight of the lead oxide (which is typically PbO), the amount of the barium sulfate in the paste composition can fall within a range from 0.1 to 1 wt. %, and more often, from 0.2 to 1 wt. %, from 0.4 to 0.8 wt. %, or from 0.5 to 0.7 wt. % of barium sulfate, based on the w eight of the lead oxide. Additionally or alternatively, the amount of the carbon black typically ranges from 0.05 to 1.5 wt. %, such as from 0.1 to 1 wt. %, from 0.1 to 0.9 wt. %, or from 0.2 to 0.8 wt. % of the carbon black, based on the w eight of the lead oxide.

[0028] Although not limited thereto, the amount of the lignin source can range from 0.05 to 1 wt. %, from 0.1 to 1 wt. %, from 0.2 to 0.8 wt. %, or from 0.2 to 0.5 wt. % of the lignin source, based on the weight of the lead oxide (which is typically PbO). Suitable lignin sources for the paste composition can include, for instance, a lignosulfonate, a sodium lignosulfonate, a potassium lignosulfonate, a magnesium lignosulfonate, a calcium lignosulfonate, or an aluminum lignosulfonate, and the like. Combinations of two or more of these lignin sources can be used in the paste composition, if desired.

[0029] The relative amounts of certain components in the paste composition also can be specified by weight ratios, such as the weight ratio of the barium sulfate to the carbon black and the w eight ratio of the barium sulfate to the lignin source. Illustrative and nonlimiting ranges for the weight ratio of the barium sulfate to the carbon black include from 10:1 to 1:10, from 5:1 to 1:5, from 6:1 to 2:1, or from 6: 1 to 3:1, while illustrative and nonlimiting ranges for the w eight ratio of the barium sulfate to the lignin source include from 10:1 to 1:10, from 5:1 to 1:5, from 5:1 to 1:1, or from 3:1 to 1.5:1.B. Electrodes and Batteries

[0030] Electrodes can be produced by drying and curing any of the paste compositions disclosed herein onto a metal current collector, which is typically lead-based. The electrode can have any suitable geometry, such as a plate, a tube, a cylinder, or a rectangular prism, and the like. Ordinarily, although not limited thereto, the electrode typically has a planar / plate geometry’ and is often referred to as an electrode plate.

[0031] An illustrative process for preparing an electrode can comprise (or an electrode can be prepared by a process comprising) contacting or reacting in any order (i) a lead oxide, (ii) a carbon black comprising an alkali metal silicate impregnated thereon, (iii) a lignin source, (iv) barium sulfate (BaSO-i). (v) sulfuric acid, and any optional ingredients to form the paste composition, and then drying and curing the paste composition onto a metal current collector to form the electrode (e.g., the electrode plate).

[0032] Drying and curing can be performed simultaneously or sequentially. Any suitable drying technique at any suitable temperature and pressure can be used, and for any suitable drying time. Often, oven drying or flash drying is used. Likewise, any suitable curing technique at any suitable temperature, pressure, and humidity can be used, and for any suitable curing time. Curing at an elevated temperature and humidity' is ordinarily used, with the curing and formation of the electrode taking place in an oven or like apparatus.

[0033] A battery containing the electrode (one or more electrodes or one or more electrode plates) also is encompassed herein. The battery can have any configuration known to those of skill in the art as well as any other components. For instance, the battery can further include a glass mat.

[0034] While not wishing to be bound by the following theory', it is believed that the utilization of a small amount of carbon black in the paste composition, and in particular, a carbon black that comprises an alkali metal silicate impregnated thereon, when converted into an electrode and utilized in a lead acid battery', can improve both the life cycle and cold cranking performance of the lead acid battery. Also, while not wishing to be bound by the following theory, it is believed that the use of silicate by itself results in a non-homogeneous paste composition, which does not occur with the use of the alkali metal silicate impregnated carbon black. Dispersion of silicate in the paste composition, and therefore in the electrode, is improved due to carbon black component. Further, the use of silicate by itself results in a strong reaction with sulfuric acid, whereas the use of the alkali metal silicate impregnatedcarbon black mediates this reaction to form a paste composition, and when converted into an electrode and utilized in a lead acid battery, increases battery lifetime. These and other electrical / battery advantages result from the use of a carbon black (comprising an alkali metal silicate impregnated thereon) as described herein.C. Carbon Black

[0035] The carbon black component of the paste composition (or formulation) comprises an alkali metal silicate impregnated thereon. In one aspect, the alkali metal silicate comprises sodium silicate, while in another aspect, the alkali metal silicate comprises potassium silicate, and in yet another aspect, the alkali metal silicate comprises both sodium silicate and potassium silicate.

[0036] The relative amounts of certain non-carbon materials on the carbon black are not particularly limited, but are generally present in amounts of less than 5 wt. %, and more often, less than 3 wt. %. For instance, based on the w eight of the carbon black, the amount of silicon (from the alkali metal silicate) can fall within a range from 0.1 to 2 wt. %, and more often, from 0.25 to 1.5 wt. %, from 0.5 to 1.25 wt. %, or from 0.5 to 1 wt. % of silicon, based on the weight of the carbon black. Additionally or alternatively, the amount of the alkali metal (from the alkali metal silicate, such as sodium and / or potassium) ty pically ranges from 0.1 to 2 wt. %, such as from 0.25 to 1.5 wt. %, from 0.5 to 1.25 wt. %, or from 0.5 to 1 wt. % of the alkali metal, based on the weight of the carbon black.

[0037] While not limited thereto, the molar ratio of alkali metaksilicon on the carbon black generally falls within a range from 0.3: 1 to 1.6: 1. In one aspect, for instance, the molar ratio of alkali metaksilicon on the carbon black can be from 0.4:1 to 1.2:1, from 0.5:1 to 1.1:1 in another aspect, from 0.6: 1 to 1 : 1 in yet another aspect, and from 0.65: 1 to 0.95:1 in still another aspect.

[0038] The carbon black (which comprises the alkali metal silicate impregnated thereon) can be prepared in any suitable manner. Generally, the carbon black is prepared by a process that comprises contacting, in any order, a base carbon black, the alkali metal silicate (e.g., sodium silicate), a dispersant, and water. In a particular aspect, the carbon black can be prepared by a process that comprises (A) contacting water and a dispersant to form a first solution, (B) contacting an alkali metal silicate solution with the first solution to form a second solution, and (C) contacting the second solution with a base carbon black to form thecarbon black. Step (C) can use a variety of techniques to impregnate the base carbon black in order to form the carbon black (which comprises the alkali metal impregnated thereon). A non-limiting example is to spray the second solution through one or more nozzles onto the base carbon black while rolling or rotating the base carbon black in a drum or tumbler, thereby forming the (alkali metal silicate impregnated) carbon black.

[0039] Any suitable dispersant can be used to prepare the (alkali metal silicate impregnated) carbon black. Illustrative and non-limiting examples of a suitable dispersant include a polyvinyl pyrrolidone (PVP), a lignin source, a lignosulfonate, humic acid, sodium citrate, a nonylphenol ethoxylate (NPE), a polyacrylic acid (PAA), a sodium polyphosphate, a polyethylene glycol (PEG), a polyvinyl alcohol (PVA), sodium dodecyl sulfate (SDS), a salt of a formaldehyde-naphthalenesulfonic acid condensate, a naphthalene sulfonic acid formaldehyde condensate, a salt of a condensed arylsulfonic acid, and the like, as well as mixtures or combinations thereof.

[0040] In circumstances where the dispersant contains sulfur, the amount of sulfur (from the dispersant) on the carbon black generally can fall within a range from 0.01 to I wt. % of sulfur. Other suitable ranges for the amount of sulfur (if present), based on the weight of the carbon black, include from 0.02 to 0.85 wt. %, from 0.04 to 0.7 wt. %, and from 0.06 to 0.6 wt. % of sulfur, based on the weight of the carbon black.

[0041] In one aspect, the carbon black (or the base carbon black) can have an iodine adsorption number, measured in accordance with ASTM DI 510, in a range from 20 to 195 mg / g, such as from 20 to 50, from 20 to 30, from 25 to 150, from 25 to 100, from 30 to 100, from 30 to 70, from 35 to 65, from 40 to 60, or from 45 to 55 mg / g. Additionally or alternatively, the carbon black (or the base carbon black) can have an oil absorption number (OAN), measured in accordance with ASTM D2414, in a range from 60 to 220 cc / lOOg, such as from 70 to 200, from 80 to 170, from 90 to 140, from 95 to 135, from 100 to 125, from 100 to 112, or from 105 to 117 cc / 100 g.

[0042] Additionally or alternatively, the carbon black (or the base carbon black) can have a nitrogen BET surface area (NSA), measured in accordance with ASTM D6556, in a range from 20 to 195 m2 / g, although not limited thereto. Other suitable ranges for the NSA include from 25 to 150, from 25 to 100, from 30 to 100, from 30 to 60, from 35 to 55, from 38 to 50, and from 40 to 47 m2 / g.

[0043] The carbon black (or the base carbon black) can have a toluene discoloration, measured in accordance with ASTM D1618, of at least 75% in one aspect, at least 78% in another aspect, at least 82% in yet another aspect, and at least 85% in still another aspect. Additionally or alternatively, the carbon black (or the base carbon black) can have a tint strength, measured in accordance with ASTM D3265, in a range from 50 to 140, from 50 to 100, from 50 to 85, from 55 to 140, from 55 to 100, from 55 to 80, from 57 to 75. or from 61 to 71 % ITRB. Additionally or alternatively, the carbon black (or the base carbon black) can have a heat loss, measured in accordance with ASTM DI 509, in a range from 5 to 30% in one aspect, from 10 to 25% in another aspect, from 12 to 27% in yet another aspect, and from 15 to 25% in still another aspect. Additionally or alternatively, the carbon black (or the base carbon black) can have an ash content, measured in accordance with ASTM D1506, that generally ranges from 0.5 to 10 wt. %, with other typical ranges including from 1 to 8, from 1.25 to 6, and from 1.5 to 4 wt. % on a dry' weight basis.

[0044] While not limited thereto, often less than or equal to 500 ppm, and more often, less than or equal to 100 ppm. less than or equal to 50 ppm, or less than or equal to 10 ppm of the carbon black (or the base carbon black) remains on a #35 sieve, measured in accordance with ASTM D1514, or has a particle size / diameter greater than 500 microns. Also while not limited thereto, often less than or equal to 1000 ppm, and more often, less than or equal to 500 ppm, less than or equal to 250 ppm, or less than or equal to 200 ppm of the carbon black (or the base carbon black) remains on a #325 sieve, measured in accordance with ASTM D1514, or has a particle size / diameter greater than 44 microns. Particle size distribution (particle size in diameter) is measured using conventional laser diffraction.

[0045] The base carbon black can comprise any suitable carbon black material. In one aspect, the base carbon black can comprise a conductive or semi-conductive carbon black. In another aspect, the base carbon black can comprise a high structure carbon black. High structure carbon blacks can increase compound viscosity, modulus, and conductivity. High structure can also reduce loading capacity, and improve dispersibility. Lower structure carbon blacks can decrease compound viscosity, increase loading capacity, but can also decrease dispersibility. If all other features of a carbon black are kept constant, narrow aggregate size distribution increases difficulty of carbon black dispersion. In yet another aspect, the base carbon black can comprise an ozonated carbon black.

[0046] The standard method for the production of the base carbon black is well known. Generally, the base carbon black is produced by the partial oxidation or thermal decomposition of hydrocarbon gases or liquids, where a hydrocarbon raw material (hereinafter called '‘feedstock hydrocarbon”) is injected into a flow of hot gas wherein the feedstock hydrocarbon is pyrolyzed and converted into a smoke before being quenched by a water spray. The hot gas is produced by burning fuel in a combustion section. The hot gas flows from the combustion section into a reaction section which is in open communication with the combustion section. The feedstock hydrocarbon is introduced into the hot gas as the hot gas flows through the reaction section, thereby forming a reaction mixture comprising particles of the base carbon black. The reaction mixture flows from the reactor into a cooling section which is in open communication with the reaction section. At some location in the cooling section, one or more quench sprays of, for example, water, are introduced into the flowing reaction mixture thereby lowering the temperature of the reaction mixture below the temperature necessary for base carbon black production and halting the carbon formation reaction. The particles are then separated from the flow of hot gas. A broad range of base carbon black A pes can be made by controlled manipulation of the reactor conditions.EXAMPLES

[0047] Various exemplary embodiments of the invention are detailed below . These embodiments are intended to be exemplary and are not intended to limit the scope of the invention.

[0048] A carbon black comprising an alkali metal silicate impregnated thereon was prepared from the components in the respective relative amounts shown in Table 1. First, 150 g of a dispersant was mixed with water and the resulting solution was then mixed with 404.3 g of a solution of 37.1 wt. % disodium metasilicate (NaeSiO?) in water. This additive solution contained approximately 945.7 g of additional w ater (not including water already present in the sodium silicate solution). The additive solution w as placed in a pressure vessel and pressurized to 60 psig with air.Table 1AmountMaterial(wt. %)Base Carbon Black 75Dispersant 2.5Sodium Silicate 2.5Water 20

[0049] Then, 4500 g of a base carbon black was placed in a 55-gallon drum oriented horizontally and rotated at 12 rpm. The base carbon black had an iodine adsorption number (ASTM D1510) of 45 to 55 mg / g, an oil absorption number (ASTM D2414) of 105 to 117 cc / 100 g, atoluene discoloration (ASTM D1618) of at least 85%, and a tint strength (ASTM D3265) of 61 to 71 % ITRB. The drum was equipped with 4 spray nozzles that were connected to the pressure vessel with the additive solution. The drum was rotated while the additive solution was sprayed onto the base carbon black over 8-15 min until the pressure vessel was empty (all the additive solution was contacted with the base carbon black). The drum was then rotated another 10 min to ensure uniform deposition.

[0050] The resulting (alkali metal silicate impregnated) carbon black was characterized by a heat loss (ASTM D1509) of 15 to 25% and an ash content (ASTM D1506) from 1.5 to 4 wt. %. Less than 5 ppm of the carbon black remained on a #35 sieve (ASTM D1514) and less than 175 ppm of the carbon black remained on a#325 sieve (ASTM D1514). The alkali metal silicate impregnated carbon black also was characterized by an iodine adsorption number (ASTM DI 510) of 20 to 30 mg / g, a nitrogen BET surface area (ASTM D6556) in a range from 40 to 47 m2 / g. an oil absorption number (ASTM D2414) of 100 to 1 12 cc / 100 g, a tint strength (ASTM D3265) of 61 to 71 % ITRB, and a d50 average laser diffraction particle size of 5 to 15 pm.ASPECTS

[0051] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other aspects of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a truescope and spirit of the invention being indicated by the following claims. Other aspects of the invention can include, but are not limited to. the following (aspects are described as “comprising’’ but, alternatively, can “consist essentially of’ or “consist of’):

[0052] Aspect 1. A paste composition (or formulation) comprising (i) a lead oxide, (ii) a carbon black comprising an alkali metal silicate impregnated thereon, (iii) a lignin source, (iv) barium sulfate (BaSC ), and (v) sulfuric acid.

[0053] Aspect 2. The composition defined in aspect 1, wherein the composition further comprises (vi) water.

[0054] Aspect 3. An electrode produced by drying and curing the paste composition defined in aspect 1 or 2 onto a metal current collector, and the electrode has any suitable geometry, such as a plate, a tube, a cylinder, or a rectangular prism, or the electrode is an electrode plate.

[0055] Aspect 4. An electrode prepared by a process comprising (a) contacting (or reacting) in any order (i) a lead oxide, (ii) a carbon black comprising an alkali metal silicate impregnated thereon, (iii) a lignin source, (iv) barium sulfate (BaSO-i). and (v) sulfuric acid, to form a paste composition, and (b) drying and curing the paste composition onto a metal current collector to form the electrode.

[0056] Aspect 5. The electrode defined in aspect 4, wherein step (a) further comprises contacting (vi) water to form the paste composition.

[0057] Aspect 6. The electrode defined in aspect 4 or 5. wherein the carbon black, the lignin source, and the barium sulfate are combined first, followed by combining the sulfuric acid (and optional water) and the lead oxide.

[0058] Aspect 7. A battery comprising the electrode defined in any one of aspects 3-6.

[0059] Aspect 8. The battery defined in aspect 7, wherein the battery further comprises a glass mat.

[0060] Aspect 9. A process for preparing an electrode (e.g., an electrode plate), the process comprising (a) contacting (or reacting) in any order (i) a lead oxide, (ii) a carbon black comprising an alkali metal silicate impregnated thereon, (iii) a lignin source, (iv) barium sulfate (BaSCh), and (v) sulfuric acid, to form a paste composition, and (b) drying and curing the paste composition onto a metal current collector to form the electrode (e.g., the electrode plate).

[0061] Aspect 10. The process defined in aspect 9, wherein step (a) further comprises contacting (vi) water to form the paste composition.

[0062] Aspect 11. The process defined in aspect 9 or 10, wherein the carbon black, the lignin source, and the barium sulfate are combined first, followed by combining the sulfuric acid (and optional water) and the lead oxide.

[0063] Aspect 12. The electrode prepared by the process defined in any one of aspects 9-11.

[0064] Aspect 13. A battery comprising the electrode defined in aspect 12.

[0065] Aspect 14. The battery defined in aspect 13, wherein the battery further comprises a glass mat.

[0066] Aspect 15. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein the lead oxide, the carbon black, the lignin source, the barium sulfate, and the sulfuric acid (and optional water) are contacted with a conductive additive (such as graphite and / or graphene), or a tetrabasic lead (such as tetrabasic lead sulfate), or both the conductive additive and the tetrabasic lead.

[0067] Aspect 16. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein an amount of the barium sulfate is in any suitable range, e.g., from 0.1 to 1 wt. %, from 0.2 to 1 wt. %, from 0.4 to 0.8 wt. %, or from 0.5 to 0.7 wt. %, based on a weight of the lead oxide.

[0068] Aspect 17. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein an amount of the carbon black is in any suitable range, e.g., from 0.05 to 1.5 wt. %, from 0.1 to 1 wt. %, from 0.1 to 0.9 wt. %, or from 0.2 to 0.8 wt. %, based on a weight of the lead oxide.

[0069] Aspect 18. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein a weight ratio of the barium sulfate to the carbon black is in any suitable range, e.g., from 10: 1 to 1:10, from 5:1 to 1:5, from 6:1 to 2:1, or from 6:1 to 3:1.

[0070] Aspect 19. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein the lignin source comprises a lignosulfonate, a sodium lignosulfonate, a potassium lignosulfonate, a magnesium lignosulfonate, a calcium lignosulfonate, an aluminum lignosulfonate, or any combination thereof.

[0071] Aspect 20. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein an amount of the lignin source is in any suitable range, e.g., from 0.05 to 1 wt. %, from 0.1 to 1 wt. %, from 0.2 to 0.8 wt. %, or from 0.2 to 0.5 wt. %, based on a weight of the lead oxide.

[0072] Aspect 21. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein a weight ratio of the barium sulfate to the lignin source is in any suitable range, e.g., from 10:1 to 1:10, from 5:1 to 1:5. from 5:1 to 1:1, or from 3:1 to 1.5:1.

[0073] Aspect 22. The composition, electrode, battery', or process defined in any one of the preceding aspects, wherein the alkali metal silicate comprises sodium silicate, or potassium silicate, or both sodium silicate and potassium silicate; and / or the lead oxide comprises PbO, PbCh, PteCh. Pb2(K or any combination thereof, or PbO.

[0074] Aspect 23. The composition, electrode, battery', or process defined in any one of the preceding aspects, wherein an amount of silicon (of the alkali metal silicate) is in any suitable range, e g., from 0.1 to 2 wt. %, from 0.25 to 1.5 wt. %, from 0.5 to 1.25 wt. %, or from 0.5 to 1 wt. %, based on a weight of the carbon black.

[0075] Aspect 24. The composition, electrode, battery', or process defined in any one of the preceding aspects, wherein an amount of the alkali metal (of the alkali metal silicate) is in any suitable range, e.g., from 0.1 to 2 wt. %. from 0.25 to 1.5 wt. %, from 0.5 to 1.25 wt. %, or from 0.5 to 1 wt. %, based on a weight of the carbon black.

[0076] Aspect 25. The composition, electrode, battery', or process defined in any one of the preceding aspects, wherein a molar ratio of alkali metahsilicon on the carbon black is in any suitable range, e.g., from 0.3:1 to 1.6:1, from 0.4:1 to 1.2: 1, from 0.5:1 to 1.1:1, 0.6:1 to 1:1, or from 0.65:1 to 0.95:1.

[0077] Aspect 26. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein an amount of sulfur (of the dispersant) is in any suitable range, e.g., from 0.01 to 1 wt. %, from 0.02 to 0.85 wt. %, from 0.04 to 0.7 wt. %, or from 0.06 to 0.6 wt. %, based on a weight of the carbon black.

[0078] Aspect 27. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein the carbon black is prepared by a process comprising contacting, in any order, a base carbon black, the alkali metal silicate (e.g., sodium silicate), a dispersant, and water.

[0079] Aspect 28. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein the carbon black is prepared by a process comprising (A) contacting water and a dispersant to form a first solution, (B) contacting an alkali metal silicate solution with the first solution to form a second solution, and (C) contacting the second solution with a base carbon black (e.g., spraying the second solution through one or more nozzles onto a base carbon black while rolling or rotating the base carbon black in a drum or tumbler) to form the carbon black.

[0080] Aspect 29. The composition, electrode, battery', or process defined in any one of the preceding aspects, wherein the dispersant comprises a polyvinyl pyrrolidone (PVP), a lignin source, a lignosulfonate, humic acid, sodium citrate, a nonylphenol ethoxylate (NPE), a polyacrylic acid (PAA), a sodium polyphosphate, a polyethylene glycol (PEG), a polyvinyl alcohol (PVA), sodium dodecyl sulfate (SDS), a salt of a formaldehydenaphthalenesulfonic acid condensate, a naphthalene sulfonic acid formaldehyde condensate, a salt of a condensed arylsulfonic acid, or any combination thereof.

[0081] Aspect 30. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein the carbon black (or the base carbon black) has an iodine adsorption number (ASTM D1510) in a range from 20 to 195, from 20 to 50, from 20 to 30, from 25 to 150, from 25 to 100, from 30 to 100, from 30 to 70, from 35 to 65, from 40 to 60, or from 45 to 55 mg / g.

[0082] Aspect 31. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein the carbon black (or the base carbon black) has an oil absorption number (ASTM D2414) in a range from 60 to 220, from 70 to 200, from 80 to 170, from 90 to 140, from 95 to 135, from 100 to 125, from 100 to 112, or from 105 to 117 cc / 100 g.

[0083] Aspect 32. The composition, electrode, battery7, or process defined in any one of the preceding aspects, wherein the carbon black (or the base carbon black) has a nitrogen BET surface area (ASTM D6556) in a range from 20 to 195, from 25 to 150, from 25 to 100, from 30 to 100, from 30 to 60, from 35 to 55, from 38 to 50, or from 40 to 47 m2 / g.

[0084] Aspect 33. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein the carbon black (or the base carbon black) has a toluene discoloration (ASTM D1618) of at least 75, at least 78, at least 82, or at least 85%.

[0085] Aspect 34. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein the carbon black (or the base carbon black) has a tint strength (ASTM D3265) in a range from 50 to 140, from 50 to 100, from 50 to 85, from 55 to 140, from 55 to 100, from 55 to 80, from 57 to 75, or from 61 to 71 % ITRB.

[0086] Aspect 35. The composition, electrode, battery, or process defined in any one of the preceding aspects, wherein the carbon black (or the base carbon black) has a heat loss (ASTM D1509) in a range from 5 to 30, from 10 to 25, from 12 to 27, or from 15 to 25%.

[0087] Aspect 36. The composition, electrode, battery', or process defined in any one of the preceding aspects, wherein the carbon black (or the base carbon black) has an ash content (ASTM DI 506) in a range from 0.5 to 10. from 1 to 8, from 1.25 to 6, or from 1.5 to 4 wt. %.

[0088] Aspect 37. The composition, electrode, battery', or process defined in any one of the preceding aspects, wherein less than or equal to 500 ppm, less than or equal to 100 ppm, less than or equal to 50 ppm. or less than or equal to 10 ppm of the carbon black (or the base carbon black) remains on a #35 sieve (ASTM D1514) (or has a particle size / diameter greater than 500 microns).

[0089] Aspect 38. The composition, electrode, battery', or process defined in any one of the preceding aspects, wherein less than or equal to 1000 ppm, less than or equal to 500 ppm, less than or equal to 250 ppm. or less than or equal to 200 ppm of the carbon black (or the base carbon black) remains on a #325 sieve (ASTM D 1514) (or has a particle size / diameter greater than 44 microns).

Claims

CLAIMSWhat is claimed is:

1. A paste composition comprising:(i) a lead oxide:(ii) a carbon black comprising an alkali metal silicate impregnated thereon;(iii) a lignin source;(iv) barium sulfate (BaSCL); and(v) sulfuric acid.

2. The composition of claim 1, wherein the composition further comprises (vi) water.

3. The composition of claim 1 or 2. wherein the composition further comprises: a conductive additive, such as graphite and / or graphene;a tetrabasic lead, such as tetrabasic lead sulfate; orboth.

4. An electrode produced by drying and curing the paste composition of any one of claims 1-3 onto a metal current collector.

5. A battery comprising the electrode of claim 4.

6. The battery of claim 5, wherein the battery further comprises a glass mat.

7. A process for preparing an electrode, the process comprising:(a) contacting in any order:(i) a lead oxide:(ii) a carbon black comprising an alkali metal silicate impregnated thereon; (iii) a lignin source;(iv) barium sulfate (BaSCL); and(v) sulfuric acid, to form a paste composition; and(b) drying and curing the paste composition onto a metal current collector to form the electrode.

8. The process of claim 7, wherein step (a) further comprises contacting (vi) water to form the paste composition.

9. The process of claim 7 or 8, wherein the carbon black, the lignin source, and the barium sulfate are combined first, followed by combining the sulfuric acid (and optional water) and the lead oxide.

10. The process of any one of claims 7-9, wherein step (a) further comprises contacting:a conductive additive, such as graphite and / or graphene;a tetrabasic lead, such as tetrabasic lead sulfate; orboth;to form the paste composition.

11. The electrode prepared by the process of any one of claims 7-10.

12. A battery comprising the electrode of claim 11.

13. The battery of claim 12, wherein the battery further comprises a glass mat.

14. The electrode, battery, or process of any one of claims 4-13, wherein the electrode is a plate, a tube, a cylinder, or a rectangular prism.

15. The composition, electrode, battery', or process of any one of the preceding claims, wherein:the lead oxide comprises PbO, PbCh, PbsC . Pb20s, or any combination thereof; the alkali metal silicate comprises sodium silicate, or potassium silicate, or both sodium silicate and potassium silicate;the lignin source comprises a lignosulfonate, a sodium lignosulfonate, a potassium lignosulfonate, a magnesium lignosulfonate, a calcium lignosulfonate, an aluminum lignosulfonate, or any combination thereof; orany combination thereof.

16. The composition, electrode, battery, or process of any one of the preceding claims, wherein:an amount of the barium sulfate is in a range from 0.1 to 1 wt. %, based on a weight of the lead oxide;an amount of the carbon black is in a range from 0.05 to 1.5 wt. %, based on a weight of the lead oxide;an amount of the lignin source is in a range from 0.05 to 1 wt. %, based on a weight of the lead oxide; orany combination thereof.

17. The composition, electrode, battery, or process of any one of the preceding claims, wherein:a weight ratio of the barium sulfate to the carbon black is in a range from 10 : 1 to 1 : 10; and / ora weight ratio of the barium sulfate to the lignin source is in a range from 10: 1 to 1 :10.

18. The composition, electrode, battery, or process of any one of the preceding claims, wherein:the lead oxide comprises PbO; andthe alkali metal silicate comprises sodium silicate.

19. The composition, electrode, battery, or process of any one of the preceding claims, wherein:an amount of silicon is in a range from 0.1 to 2 wt. %, based on a w eight of the carbon black;an amount of alkali metal is in a range from 0.1 to 2 wt. %, based on a weight of the carbon black;a molar ratio of alkali metaksilicon on the carbon black is in a range from 0.3: 1 to 1.6:1;an amount of sulfur is in a range from 0.01 to 1 wt. %, based on a weight of the carbon black; orany combination thereof.

20. The composition, electrode, battery, or process of any one of the preceding claims, wherein the carbon black is prepared by a process comprising contacting, in any order, a base carbon black, the alkali metal silicate, a dispersant, and water.

21. The composition, electrode, battery, or process of any one of the preceding claims, wherein the carbon black is prepared by a process comprising:(A) contacting water and a dispersant to form a first solution;(B) contacting an alkali metal silicate solution with the first solution to form a second solution; and(C) contacting the second solution with a base carbon black to form the carbon black.

22. The composition, electrode, battery, or process of claim 20 or 21. wherein the dispersant comprises a polyvinyl pyrrolidone (PVP), a lignin source, a lignosulfonate, humic acid, sodium citrate, a nonylphenol ethoxylate (NPE), a polyacrylic acid (PAA), a sodium polyphosphate, a polyethylene glycol (PEG), a polyvinyl alcohol (PVA), sodium dodecyl sulfate (SDS), a salt of a formaldehyde-naphthalenesulfonic acid condensate, a naphthalene sulfonic acid formaldehyde condensate, a salt of a condensed arylsulfonic acid, or any combination thereof.

23. The composition, electrode, battery, or process of any one of the preceding claims, wherein the carbon black (or the base carbon black) has:an iodine adsorption number (ASTM DI 510) in a range from 20 to 195 mg / g: an oil absorption number (ASTM D2414) in a range from 60 to 220 cc / 100 g;a nitrogen BET surface area (ASTM D6556) in a range from 20 to 195 m2 / g;atoluene discoloration (ASTM D1618) of at least 75%;a tint strength (ASTM D3265) in a range from 50 to 140 % ITRB;a heat loss (ASTM D1509) in a range from 5 to 30%;an ash content (ASTM D1506) in a range from 0.5 to 10 wt. %; orany combination thereof.

24. The composition, electrode, battery, or process of any one of the preceding claims, wherein:less than or equal to 500 ppm of the carbon black (or the base carbon black) remains on a #35 sieve (ASTM D1514) or has a particle size / diameter greater than 500 microns; and / orless than or equal to 1000 ppm of the carbon black (or the base carbon black) remains on a #325 sieve (ASTM D1514) or has a particle size / diameter greater than 44 microns.

Images