electrode and electrical storage device for lead acid based system

专利摘要:
electrode and electrical storage device for lead acid-based system the present invention relates generally to electrodes for use in lead acid battery systems, batteries and electrical storage devices therefor, and methods for producing electrodes, batteries and electrical storage devices. in particular, the electrodes comprise active battery material for a lead acid storage battery, wherein the electrode surface is provided with a coating layer comprising a carbon mixture containing composite carbon particles, wherein each of the carbon particles Composite particles comprise a particle of a first capacitor carbon material combined with particles of a second electrically conductive carbon material. the electrical storage devices and batteries comprising the electrodes are, for example, particularly suitable for use in hybrid electric vehicles that require a repeated rapid charge / discharge operation in the psoc, inactivity-stop system vehicles, and in industrial applications such as wind power generation and photovoltaic power generation.
公开号:BR112013015499B1
申请号:R112013015499
申请日:2011-12-21
公开日:2020-01-28
发明作者:Jun Furukawa；Daisuke Momma；Trieu Lan Lam；Rosalie Louey；Peter Nigel Haigh
申请人:Commonwealth Scientific And Industrial Research Organisation；The Furukawa Battery Co., Ltd.；
IPC主号:

专利说明:

ELECTRIC AND ELECTRICAL STORAGE DEVICE FOR ACID LEAD BASED SYSTEM
FIELD OF THE INVENTION
The present invention relates generally to electrodes for use in lead acid battery systems, batteries and electrical storage devices therefor, and methods for producing electrodes, batteries and electrical storage devices.
The electrical storage devices and batteries comprising the electrodes are, for example, particularly suitable for use in hybrid electric vehicles that require a repeated rapid charge / discharge operation in the partial charge state (PSOC), inactivity-stop system vehicles, and in industrial applications such as wind power generation and photovoltaic power generation.
BACKGROUND OF THE INVENTION
PCT International publication WO2005 / 027255 refers to a lead acid storage battery comprising a negative electrode, which is suitable for use in a hybrid electric vehicle requiring repeated short periods of charge / discharge operation in the PSOC. The electrode is coated with a porous carbon mixture prepared by forming a paste from a binder material and a mixed powder comprising particles of a carbon material having a capacitor capacity and / or a pseudocapacitor capacity and particles of a carbon material having electrical conductivity, which is then applied to the surface of the electrode plate and dried.
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2/50
The lead acid storage battery described in WO2005 / 027255 provides an extended life cycle compared to a lead acid storage battery provided with a conventional negative plate. However, it has been found that as the charge / discharge cycle is repeated, Pb or PbSO4 is deposited on the particle surfaces of the carbon material with a capacitor function and the entrances to various interior pores of the particles become clogged with Pb or PbSO4 deposited, so that the capacitor function is significantly impaired and, consequently, the fast charge / discharge life cycle in the PSOC is shortened.
More particularly, in relation to particles of carbon material with a capacitor function, such as activated carbon or the like contained in the conventional carbon mixture coating layer, when the battery is charged to cause polarization in the negative lead plate acid for an open circuit arrangement, the material is negatively charged and adsorbs double layer electric protons and cations with a positive charge, and when the battery is discharged cause polarization on the negative lead acid plate to an open circuit arrangement, the surfaces of the particles desorb them. In addition, when the battery is still discharged to cause polarization in the negative lead acid plate (in relation to an open circuit arrangement) then the potential when not charged, the surfaces of the particles are positively charged and adsorb anions in the electrical double layer.
Thus, in the particles of carbon material with a
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3/50 capacitor function, Pb ions as cations as well as protons are simultaneously adsorbed or desorbed. Therefore, the Pb ions adsorbed on the activated carbon surface are reduced to Pb metal, and the Pb metal is deposited on the surfaces of the particles. In addition, the discharge operation causes the oxidation of Pb, which results in the deposition of PbSO4 on the particle surfaces. These particles have inner pores and therefore have a huge internal surface area, but they have a spherical or smooth polyhedron exterior shape with apparently small surface area. Therefore, when deposition of Pb or PbSO4 on the outer surfaces of these particles occurs, the interior pore entrances are clogged with the deposited Pb or PbSO4, so that the capacitor function is significantly impaired.
There is a need for alternative and improved electrodes for use in lead acid battery systems, such as electrodes and batteries that improve the life cycle and improve some of the disadvantages of supplying high-rate materials in lead acid systems, especially in systems that require repeated short periods of loading / unloading operation on the PSOC.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides an electrode comprising active battery material for a lead acid storage battery, wherein the electrode surface is provided with a coating layer comprising a carbon mixture containing composite carbon particles. Each of the carbon particles composed
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4/50 comprises a particle of a first capacitor carbon material coated with particles of a second electrically conductive carbon material.
In another embodiment, each of the composite carbon particles may comprise, or consist of, particles of the second electrically conductive carbon material, and, optionally, the third electrically conductive material, coated on the surface of a particle of the first capacitor carbon material, wherein the surface coverage on the particles of the first capacitor carbon material by the second electrically conductive carbon material, and, optionally, the third electrically conductive material, is at least 20%.
In one embodiment, the composite carbon particles contain, or consist of, one or more particles of a first capacitor carbon material in which each of the particles is coated with particles of a second electrically conductive carbon material and, optionally, particles of a third electrically conductive carbon material. In another embodiment, the carbon mixture containing the composite carbon particles can consist of a first capacitor carbon material, a second electrically conductive carbon material, and, optionally, a third electrically conductive carbon material. For example, particles of the second electrically conductive carbon material and, optionally, particles of a third electrically conductive carbon material, can be coated on at least a substantial portion of the surface of a particle of the first carbon material
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5/50 capacitor. The particle size of the second carbon material, and optional third carbon material, can be selected to be smaller than the particle size for the first capacitor carbon material so that the electrical conductivity and the surface area of the particle composite carbon are improved compared to a particle of a first capacitor carbon material by itself.
In another embodiment, each of the composite carbon particles comprises, or consists of particles of the second electrically conductive carbon material, and, optionally, the third electrically conductive material, coated on the surface of a particle of the first capacitor carbon material. The particle surface coverage of the first capacitor carbon material by the second electrically conductive carbon material (and optionally the third electrically conductive material)
can be at least 20%, fur any less 30%, fur minus 40%, fur least 50%, at least minus 60%, fur any less 70%, at least 80%, at least 90% or fur any less 95%. The coverage of
The particle surface of the first capacitor carbon material by the second electrically conductive carbon material (and optionally the third electrically conductive material) can be in the range of 20% to 99%, 40% and 98%, 60% to 95%, 70% 95%, or 80% to 95%.
In one embodiment, the particle size of the second electrically conductive carbon material is one fifth or less than that of the first capacitor carbon material. In a preferred embodiment, the particle size of the second carbon material electrically
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6/50 conductor is one tenth or less than that of the first carbon capacitor material.
The first capacitor carbon material can be selected from at least one activated carbon and carbon black. In one embodiment, the first capacitor carbon material is activated carbon. The first capacitor carbon material may be a high specific surface area carbonaceous material. The first carbon capacitor material can have a specific surface area of at least 500 m ² / g, measured by adsorption using BET isotherm and preferably at least 1000 m ² / g.
The second electrically conductive carbon material can be selected from at least one carbon black, graphite, glassy carbon, and a nanocarbon fiber. The nanocarbon fiber can be selected from a carbon nanowire, a carbon nanotube or a carbon fiber. In one embodiment, the second electrically conductive carbon material is carbon black. Carbon black can be selected from at least one acetylene black, oven black and ketjen black. The second electrically conductive carbon material may be an elevated electrically conductive carbonaceous material. The second electrically conductive carbon material can have a conductivity of at least 0.6 Scm ^-1 at 500 kPa measured at 20 ° C.
In one embodiment, the particle size of the first capacitor carbon material is at least 1 pm, and the particle size of the second electrically conductive carbon material is one tenth or less than that of the
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7/50 first carbon capacitor material.
In one embodiment, the carbon mixture further comprises a third electrically conductive carbon material. The third electrically conductive carbon material can be selected from carbon black, graphite, glassy carbon, or a nanocarbon fiber. The nanocarbon fiber can be selected from a carbon nanowire, a carbon nanotube, or a carbon web. In one embodiment, the third electrically conductive carbon material is a vapor-growing nanocarbon fiber.
In another embodiment, the first capacitor carbon material is activated carbon, the second electrically conductive carbon material is carbon black, and the third electrically conductive carbon material is a nanocarbon fiber.
In another embodiment, the coating layer of the carbon mixture is composed of 4 to 100 parts by weight of the second electrically conductive carbon material in relation to 100 parts by weight of the first capacitor carbon material. The coating layer of the carbon mixture may additionally comprise 50 parts by weight, or less, of the third electrically conductive carbon material with respect to 100 parts by weight of the first capacitor carbon material. The coating layer of the carbon mixture may further comprise 2 to 30 parts by weight of a binder with respect to 100 parts by weight of the first capacitor carbon material.
In a particular embodiment, the coating layer
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8/50 of the carbon mixture consists of 4 to 100 parts by weight of the second electrically conductive carbon material in relation to 100 parts by weight of the first capacitor carbon material, 50 parts by weight or less of the third electrically conductive carbon material carbon, 2 to 30 parts by weight of a binder, 20 parts by weight or less to a thickener, and 20 parts by weight or less to a short fiber compared to 100 parts by weight of the first capacitor carbon material.
In another embodiment, the amount of the carbon mixture for the electrode coating layer is 1 to 15% by weight relative to the weight of the active battery material on the electrode.
The electrode can be a negative electrode comprising negative active battery material for a lead acid storage battery. The electrode can be a positive electrode containing the positive active battery material for a lead acid storage battery.
The carbon mixture for the electrode can contain composite carbon particles produced by at least one of grinding, granulating and unification, the particles of the first capacitor carbon material with at least the particles of the second electrically conductive carbon material. Grinding may involve ball or granule grinding. The carbon mixture can contain particles of a first capacitor carbon material with particles of a second electrically conductive carbon material and, optionally, particles of a third electrically conductive carbon material.
In another aspect, the present invention provides an
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9/50 hybrid negative plate for a lead acid storage battery, where the surface of a negative plate is provided with a coating layer of a carbon mixture containing carbon particles composed each comprising a particle of a first carbon material having a capacitor capacity and / or a pseudocapacitor capacity and particles of a second carbon material having electrical conductivity coverage and matching the particle surface of the first carbon material.
In one embodiment, the particle size of the second carbon material is one-tenth or less than that of the first carbon material. In another embodiment, the carbon mixture is prepared by adding a third carbon material having high electrical conductivity to the hybrid carbon particles and mixing them is coated on the negative plate. The first carbon material can be activated carbon or carbon black, the second carbon material can be selected from carbon black, graphite, glassy carbon, a carbon nanowire, a carbon nanotube or a carbon triz, and the third carbon material can be selected from carbon black, graphite, glassy carbon, a carbon nanowire, a carbon nanotube, or a carbon fiber. In another embodiment, the carbon blend layer may comprise the composite carbon particles containing 4 to 100 parts by weight of the second carbon material in relation to 100 parts by weight of the first carbon material, 50 parts by weight or less at third carbon material, 2 to 30 parts by weight of a binder, 20 parts by weight or
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10/50 less to a thickener, and 20 parts by weight or less to a short fiber compared to 100 parts by weight of the first carbon.
In another embodiment, the amount of the carbon mixture for coating on the surface of the negative plate is 1 to 15% by weight in relation to the weight of negative active material on the negative plate.
The present invention also provides an electrical storage device for a lead acid based system comprising electrodes as described in the above aspects or embodiments of the invention. The electrical storage device may be a lead acid storage battery.
BRIEF DESCRIPTION OF THE DRAWINGS
The preferred embodiments of the present invention will now be further described and illustrated, by way of example only, with reference to the accompanying drawings, in which:
Figure 1 (a) provides scanning electron micrographs showing particles of the first activated carbon capacitor carbon material (representations i, ii and iii);
Figure 1 (b) provides scanning electron micrographs showing a particle agglomeration of the second electrically conductive carbon material of acetylene black (representations iv, v and vi);
Figure 2 (a) provides scanning electron micrographs showing composite hybrid carbon particles produced from a first activated carbon capacitor carbon material (100 parts per
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11/50 weight) and a second electrically conductive carbon material of acetylene black (60 parts by weight) of Example 1 (note for representations (viii) and (ix), the same magnification of the microphotographs is used in Figure 2 (b ) for representations (x) and (xi) respectively, or 5000 x or x 10000); and
Figure 2 (b) provides scanning electron micrographs showing mixed particles of a first capacitor carbon material (100 parts by weight) and a second electrically conductive carbon (60 parts by weight) from Comparative Example 1 (note for representations (x) and (xi), the same magnification of the microphotographs is used in Figure 2 (a) for the representations (viii) and (ix), respectively, or x 5000 or x 10000).
DETAILED DESCRIPTION
The present invention will be further described with reference to preferred embodiments, which are provided by way of example only.
The aspects and embodiments of the present invention provide a number of advantages over conventional or known lead acid battery systems. The advantages provided by at least some of the preferred modalities are described as follows.
A hybrid or improved electrode is produced by providing a coating layer comprising a carbon mixture containing the composite carbon particles as described herein. Electrodes are typically formed using a metal plate that comprises an active battery material, in which the materials being used can be selected to provide a negative electrode
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12/50 or positive for a lead acid based system. Typical electrical storage devices for lead acid based systems involve lead acid batteries comprising at least one positive electrode and at least one negative electrode of a sulfuric acid electrolyte solution.
An electrical storage device or lead acid storage battery comprising an electrode containing a coating layer comprising the composite carbon particles can provide an extended life cycle, in particular if a rapid charge / discharge operation on the PSOC is repeated. needed.
Composite Carbon Particles
The composite carbon particles used in a coating layer for the electrodes each comprise a particle of a first capacitor carbon material coated with particles of a second electrically conductive carbon material, and, optionally, a third electrically conductive carbon material.
The particles of the second carbon material cover the surface of the particles of the first carbon material. The coating can be such that the first and second carbon particles are considered to cover, combine or adhere together. The composite carbon particles are then typically covered on an electrode surface like a paste (including other materials) to produce an improved electrode, which can also be referred to as a hybrid electrode. In a lead acid storage battery provided with the electrode
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13/50 hybrid of the invention, even when the charge / discharge operation is repeatedly performed, the particle surface of the first capacitor carbon material is protected by the particles of the second electrically conductive carbon material and, optionally, particles of a third material electrically conductive carbon. The particles of the second electrically conductive carbon material (and the third electrically conductive carbon material, if present) cover the particle surface of the first capacitor carbon material to reduce or suppress pore clogging in the particles of the first capacitor carbon material by deposited Pb or PbSO4. Thus, compared to a conventional lead acid storage battery, the life cycle is surprisingly improved for a lead acid storage battery equipped with an electrode (also referred to as a hybrid electrode or plate) that is supplied with a layer of coating a carbon mixture comprising carbon particles composed of the first capacitor carbon material coated with particles of the second electrically conductive carbon material (and third electrically conductive carbon material, if present).
The composite carbon particles can contain, or consist of, one or more particles of a first capacitor carbon material in which each of the particles is coated with particles of a second electrically conductive carbon material and, optionally, particles of a third electrically conductive carbon material. For example, the particles of the second carbon material
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14/50 electrically conductive and, optionally, particles of a third electrically conductive carbon material, can cover and adhere to at least a substantial portion of the surface of a particle of the first capacitor carbon material. The particle size of the second carbon material, and optional third carbon material, can be selected to be smaller than the particle size for the first capacitor carbon material to allow coating, and can be selected such that the electrical conductivity and surface of the composite carbon particle are improved over a particle of a first capacitor carbon material. The smaller particle size for the second and third carbon materials can provide effective face contact between the particles and allow good electrical conduction between the particles. In relation to a particle of a first capacitor carbon material per se, the larger surface area of the composite carbon particle, provided by the smaller particle size of the second and third carbon materials, also attenuates, in use, the clogging of the first capacitor material from Pb and PbSO4.
It should be noted that the coating adhesion of the second electrically conductive (and optionally third) carbon material to the surface of the first capacitor carbon material can typically involve an intermolecular surface interaction, for example, dipole-dipole interactions, such as van der Waals interaction forces and London dispersion or pi connection interactions.
In one embodiment, the particles of the second material
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15/50 of electrically conductive carbon and, optionally, particles of a third electrically conductive carbon material, can be coated with at least a substantial portion of the surface of a particle of the first capacitor carbon material.
In another embodiment, each of the composite carbon particles comprises, or consists of particles of the second electrically conductive carbon material (and optionally the third electrically conductive material) coated on the surface of a particle of the first capacitor carbon material.
The particle surface coverage of the first capacitor carbon material by the second electrically conductive carbon material (and optionally the third electrically conductive material) can be at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90% or at least 95%. The particle surface coverage of the first capacitor carbon material by the second electrically conductive carbon material (and, optionally, the third electrically conductive material) can be in the range of 20% to 99%, 40% and 98%, 60% at 95%, 70% to 95%, or 80% to 95%.
It will be appreciated that the particle surface coverage of the first carbon material by the second carbon material refers to the average amount of coverage on the outer surface of a representative sample of the composite carbon particles. A representative area of the outer surface of a composite carbon particle can, for example, be identified
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16/50 using scanning electron microscopy (SEM), and the mean particle surface area of a first capacitor carbon material coated with particles of a second carbon material can be measured, such as by visual and computational analysis. It will be appreciated that several other analysis techniques can be used to determine the surface coverage of the smaller particles by coating the larger particles.
In another embodiment, the weight% ratio of the first capacitor carbon material to the second electrically conductive carbon material in the composite carbon particles can be in the range of 25: 1 to 1: 1, 20: 1 to 10: 9, 15: 1 to 10: 8, 10: 1 to 10: 7 or 5: 1 to 10: 6. In another embodiment, the weight% ratio of the first capacitor carbon material to the second electrically conductive carbon material in the composite carbon particles is at least 2: 1, at least 3: 1, or at least 4 :1. If the optional third electrically conductive carbon material is present, then the weight% ratio of the first capacitor carbon material to the third electrically conductive carbon material in the composite carbon particles can be less than 1: 2, less than 1 : 3, less than 1: 4, or less than 1: 5. An advantage provided by the composite carbon particles is that a relatively lower amount of electrically conductive carbon black material can be used in the carbon mixture while, in use, it achieves high performance.
For the production of composite carbon particles where the particle surface of the first carbon material
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17/50 capacitor carbon is combined with the particles of the second electrically conductive carbon material having a smaller particle size (than that of the first carbon material), a grinding apparatus, such as a granule mill or a grinder. a sphere, a granulation apparatus, or a unification apparatus such as a mechanofuser or a hybridizer may be used. Hybrid or composite carbon particles can be produced using a laser, arc discharge, an electron beam, or the like, although these methods are expensive. Other methods can achieve a coating or surface adhesion of the particles of the second carbon material to a particle of the first carbon material such that they provide a composite carbon material.
In this particle unification treatment, it has been shown that an effective coating can be obtained using the second electrically conductive carbon material having a particle size that is one tenth or less than the particle size of the first capacitor carbon material.
In the scanning electron micrographs of Figures 1 (a) and 1 (b), the differences can be seen in the morphology and size between the first capacitor carbon material, that is, the activated carbon in Figure 1 (a) and the second electrically conductive carbon, namely acetylene black of Figure 1 (b). The first capacitor carbon material has individual particles (representations (i), (ii) and (iii)), while the second electrically conductive carbon material has clusters of particles
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18/50 minors (see representations (iv), (v) and (vi)). It should be noted that the pores of the first capacitor carbon material are unable to be observed by scanning electron microscopy, although they can be analyzed using electron transmission microscopy or atomic force microscopy. It will be appreciated from Figures 1 (a) and 1 (b) that the particle sizes of the first capacitor carbon material are substantially larger than the particles of the second electrically conductive carbon material. In the particular embodiment provided in Figures 1 (a) and 1 (b), the average particle size of the first capacitor carbon material is about 8 pm, while the second electrically conductive carbon material is about 0, 1 pm.
Figures 2 (a) and 2 (b) show the differences between a carbon mixture containing the composite carbon particles (see Figure 2 (a) and in Example 1 below) and a carbon mixture comprising a simple mixture of the first material capacitor carbon and the second capacitor carbon material (see Figure 2 (b) and Comparative Example 1 below). In contrast to the mixed material of Figure 2 (b), the carbon particles composed in Figure 2 (a) show that the comparatively smaller second electrically conductive carbon particles cover a substantial portion of the surface of the first carbon material, for example, at least 20% and up to about 95% of the surface of the first capacitor carbon material.
In contrast to the carbon particles composed of the
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19/50
Figure 2 (a), the mixed material of Figure 2 (b) shows that there is a relatively weaker or lesser coating, adhesion or surface coverage, of the second carbon particles on the surface of the first carbon particles. It can be seen in Figure 2 (b) that the particles of the second carbon material exist mainly between the first carbon particles, indicating poor coating, adhesion or surface coverage, for example the covering of the second carbon particles on the surface of the first particles carbon can be less than about 5% of the mixed material. The coating and surface coverage of the second carbon particles in the first carbon particles in the composite carbon particles allows a mixture of paste or coating, produced from a mixture of carbon containing the composite carbon particles, to obtain better performance characteristics relative to the simply mixed material.
It will be appreciated that the coating layer comprises a degree of porosity to allow permeability for a liquid electrolyte. For example, adequate porosity can be in the range of 40 to 85%. In a particular embodiment, the porosity of the coating layer is about 75%.
First capacitor carbon material
The first capacitor carbon material is selected from a carbon material that has the capacitor capacity and / or the pseudocapacitor capacity, for example, activated carbon. It will be appreciated that the first carbon capacitor material
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20/50 must be sufficiently stable in lead acid battery electrolyte solutions, such as sulfuric acid electrolyte solutions.
The first capacitor carbon material can be a high-rate electroactive material, which can be of any high-rate (or high-power) carbon-based material that generally presents the characteristics of capacitors. Such materials are well known in the art, such as high surface area carbon. These materials typically provide a high rate or high initial power output of a short duration, but have a lower energy density compared to a high energy material, such as active battery material that typically provides a greater amount of energy or more sustained, but at a lower rate. Examples of high surface area carbon materials are activated carbon, carbon black, amorphous carbon, carbon nanoparticles, carbon nanotubes, carbon fibers and mixtures thereof.
In a preferred embodiment, the first capacitor carbon material is selected from at least one activated carbon, and carbon black. In another embodiment, the first carbon material is activated carbon.
Types of activated carbons that can be used as the first capacitor carbon material include various types of activated carbon, such as those derived from synthetic resins, those derived from natural wood materials such as coconut shell, wood, sawdust, carbon vegetable, lignin etc, those derived from
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21/50 carbon, such as legnite and peat, etc., and oil derivatives. Carbon black includes acetylene black, oven black, and ketjen black.
The first capacitor carbon material may be a high surface area carbon or high specific surface area carbonaceous material. The term carbonaceous material with a high specific surface area is well known and commonly used in the art. Specific surface area refers to a total surface area per unit of mass. This is usually measured by absorption using the BET isotherm. Thus, references to a BET surface area are made for a specific surface area. In addition, references to a property measured in units of m ² / g are made for a specific surface area. With regard to high expression, it is normally understood in the art of the invention that certain types of materials that are used as components of electrochemical devices fall into a category known as high surface area or specific high surface area materials. An elevated specific surface area refers to a surface area that can be above about 500 m ² / g, and more typically above about 1000 m ² / g.
A surface area for the first carbon capacitor material can be at least 500 m ² / g, and more typically in the range of about 1000 m ² / g and 3500 m ² / g. In various embodiments, the surface area of the first capacitor carbon material can be at least 1000 m ² / g, at least 1500 m ² / g, at least 2000
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m ² / g, or in a range of 500 to 8000 m ² / g, from 800 to 5000 m ² / g, from 1000 to 3500 m ² / g, or of 1500 at 3000 m ² / g.
The particle size of the second electrically conductive carbon material is smaller than the particle size of the first capacitor carbon material so that the second carbon material can coat the surface of the first carbon material to, in use, suppress or reduce the clogging of the particles surface of the first carbon material, which can occur, for example, by deposition of Pb or PbSO4. In addition, the second electrically conductive carbon material increases the electrical conductivity between the composite carbon particles.
The second electrically conductive carbon material can have a particle size that is one fifth or less, one tenth or less, one twentieth or less, or one fiftieth or less, than that of the first carbon material. In a preferred embodiment, the second carbon material has a particle size that is one-tenth or less than that of the first carbon material. For example, when the first carbon material has a particle size of 3 to 30 pm, the second carbon material can have a particle size of 0.3 to 3 pm.
The particle size of the first capacitor carbon material can be less than 500 pm, less than 300 pm, less than 100 pm, less than 50 pm, less than 30 pm, less than 10 pm, or less than 5 µm. The particle size of the first carbon capacitor material can be at least 0.1 pm, at least 1 pm, at least
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23/50 pm, at least 5 um, or at least 10 pm. The particle size of the first capacitor carbon material can be in the range 0.1 to 500 pm, 1 to 100 pm, 1 to 50 pm, or 3 to 30 pm.
Various techniques can be used by one skilled in the art to determine the morphology or composition of a carbon mixture, including the presence or nature of the composed carbon particles. For example, methods may include electron energy loss spectroscopy (EEES), x-ray photoelectron spectroscopy (XPS) and scanning electron spectroscopy (SEM). Reference materials can be used and observation / correlation tests or performance or morphology comparisons performed. It will be appreciated that amorphous carbon materials, which can be distinguished based on particle size, porosity, specific surface area, can also be distinguished on the basis of other aspects such as graphite / diamond grade / nature (SP2 / SP3) of the material, which, for example, can be measured using Raman spectroscopy.
Second electrically conductive carbon material
The second electrically conductive carbon material is selected from a carbon material with electrical conductivity. It will be appreciated that the second carbon material should be adequately stable in lead acid battery electrolyte solutions, such as sulfuric acid electrolyte solutions.
In one embodiment, the second carbon material can be selected from a material with high electrical conductivity, such as a material referred to as
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24/50 a carbonaceous material with high electrical conductivity. It will be appreciated that a smaller particle size generally provides a larger surface area for a given weight and porosity.
Typically, the conductivity of the second carbon material can be at least 0.6 Scm ^-1 at 500 kPa, at least 0.19 Scm ^-1 at 1000 kPa, and at least 3.0 Scm ^-1 at 1500 kPa. These are measured at room temperature (20 ° C). The conductivity of the material can be measured using the following conductivity test method:
i. Collect 20g of sample of the material to be tested.
ii. Deposit a tubular conductivity test cell having a cross-sectional area of 1 cm ² on a metal cell base. Note, for larger particles, a tubular test cell having a larger cross-sectional area can be used, as described below. Carefully pack the conductivity test cell with about 2g of the sample to be tested. Seal the top of the conductivity test cell with the metal plunger. Touch down gently until sufficient sample fills the cell to a height of 1 cm.
iii. Place the sample cell onto the punch press so that the plunger can press against the sample when a force is applied.
iv. Apply a load to the cell. Take a multimeter reading the conductivity in the compression force measured for this load.
v After the test, remove all the traces gives sample a leave gives cell of test. (This can to be achieved through in a brush bottle and paper in
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25/50 fine sand.) Note that the conductivity of the sample at multiple compressive forces can be tested by adding the following steps between steps iv. and v above:
saw. Add more carbon powder at the top of the test cell back up to an inch, if necessary.
vii. Apply the next load required to test the conductivity of the sample under increasing compressive strength. Repeat as needed.
The second electrically conductive carbon material can be selected from at least one carbon black, glassy carbon, graphite, and a nanocarbon fiber. The nanocarbon fiber can be selected from a carbon nanotube, a carbon fiber, or a carbon nanowire. Each of these materials can provide electrical conductivity, and can be bonded under pressure (for example, by grinding) to the particle surface of the first capacitor carbon material.
The particle size of the second electrically conductive carbon material is smaller than the particle size of the first capacitor carbon material, as described above, such that the particles of the second carbon material can coat the particles of the first carbon material. capacitor carbon, and in use, to facilitate electrical conductivity between composite carbon particles while suppressing or reducing clogging of the first carbon material, which can occur by deposition of Pb or PbSO4. For example, a composite carbon particle comprises particles of a second electrically conductive carbon material adhered to the surface of a particle of a first carbon material.
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26/50 capacitor carbon, or at least a substantial portion of its surface.
The particle size of the second electrically conductive carbon material may be less than 100 pm, less than 50 pm, less than 10 pm, less than 5 µm, less than 1 pm, less than 0.1 pm, or less than 0, 01 pm, or in an interval between 0.01 to 50 pm, between 0.01 to 10 pm, between 0.01 to 5 um, or between 0.3 to 3 pm.
For a nanocarbon fiber, such as a carbon nanowire material, it can have a diameter in the range between 0.005 pm and 100 pm, between 0.005 pm and 50 pm, between 0.01 pm and 20 pm between, or between 0, 01 pm and 10 pm. In a preferred embodiment, the diameter is between 0.01 pm and 10 pm. The nanowire length can be between 1 pm and 3000 pm, between 10 pm and 2000 pm, between 20 pm and 1000 pm, between 30 and 5 mm 500 mm, or between 50 pm and 100 pm. In a preferred embodiment, the length is between 50 pm and 100 pm.
For a carbon nanotube material, the diameter can be in the range between 0.005 pm and 100 pm, between 0.01 pm and 50 pm between, or between 0.01 pm and 30 pm. In a preferred embodiment, the diameter is between 0.01 pm and 30 pm. The length of the nanotube can be between 1 pm and 3000 pm, between 10 pm and 2000 pm, between 20 pm and 1000 pm, between 30 mm and 500 mm, or between 50 pm and 100 pm. In a preferred embodiment, the length is between 50 pm and 100 pm.
A suitable surface area for the second electrically conductive carbon material can be in the range of about 200 to 1500 m ² / g. In various embodiments, the surface area of the second
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27/50 carbon can be at least 100 m ² / g, at least 2 00 m ² / g, at least 500 m ² / g, or in a range of 100 to 2,000 m ² / g, 200 to 1500 m ² / g, from 300 to 1200 m ² / g, or from 500 to 1000 m ² / g.
The ratio between the mixed amount of the first capacitor carbon material and the second electrically conductive carbon material is preferably 4 to 100 parts by weight of the second carbon material in relation to 100 parts by weight of the first carbon material. However, it will be appreciated that certain advantages may still be provided outside the ranges described herein. For example, the ratio between the mixed amount of the first carbon material and the second carbon material can be, by weight of the second carbon material in relation to 100 parts by weight of the first carbon material, 10 to 90 parts of the second material of carbon, 10 to 80 parts of the second carbon material, or 20 to 70 parts of the second carbon material.
With respect to the relationship between the mixed amount of the first capacitor carbon material and the second electrically conductive carbon material to produce the composite carbon particles, as mentioned above, the second carbon material can be used in the range of 4 to 100 parts by weight, relative to 100 parts by weight of the first carbon material. If the amount of the second carbon material is less than 4 parts by weight, a satisfactory life cycle improvement effect may not be obtained. If the amount of the second carbon material exceeds 100 parts by weight, the electrical conduction effect can become
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28/50 saturated. It is preferred that the amount of 10 to 80 parts by weight of the second carbon material is mixed with respect to 100 parts by weight of the first carbon material and the mixture is combined together to obtain the composite carbon particles.
Third electrically conductive carbon material
The composite carbon particles may comprise a third electrically conductive carbon material to improve the electrical conductivity (and electrical connection) of the composite carbon particles and their coating layer. It will be appreciated that the third electrically conductive carbon material should be adequately stable in lead acid battery electrolyte solutions, such as sulfuric acid electrolyte solutions. The conductivity of the third electrically conductive carbon material may be similar to that provided above for the second electrically conductive carbon material, or it may be more electrically conductive than that of the second electrically conductive carbon material.
In one embodiment, the third electrically conductive carbon material can be selected from a material with high electrical conductivity, such as a material referred to as a carbonaceous material with high electrical conductivity.
The third electrically conductive carbon material can be selected from at least one carbon black, graphite, glassy carbon, and a nanocarbon fiber. The nanocarbon fiber can be selected from a carbon nanowire, a carbon nanotube or a carbon fiber. It will be appreciated that other materials
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29/50 can be used as the third electrically conductive carbon material.
With regard to the size of the third electrically conductive carbon material, where the third carbon material is in the form of particles, in one embodiment the particle size of the third carbon material may be smaller than that of the first carbon material capacitor. The particle size of the third electrically conductive carbon material can be similar in size to the second carbon material, as described above. Preferably, the particle size of the third electrically conductive carbon material is one tenth or less than that of the first carbon material.
In one embodiment, the particle size of the third electrically conductive carbon material is smaller than the particle size of the first electrically conductive carbon material.
capacitor, and can be less than 100 pm, less than 50 pm, less than 10 pm, less than 5 um, less than 1 pm, less than 10 to 0.1 pm, or less than 0.01 pm, or at the range between 0.01 to 50 pm, between 0.01 to 10 pm, in between 0.01 to 5 µm, or between 0.3 to 3 pm.
To further increase the electrical conductivity between the composed carbon particles, the amount of the third electrically conductive carbon material is preferably 50 parts by weight or less, relative to 100 parts by weight of the first capacitor carbon material. If the quantity of the third carbon material exceeds 50 parts by weight, the electrical conduction effect can become saturated, and, consequently, the quantity of the third carbon material is advantageously 50
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30/50 parts by weight or less, from an economic point of view, but 40 parts by weight or less is more preferable.
Coating layer
A bonding agent, that is, a binder, can be used to increase bonding of the carbon mixture to the surface of the negative plate, and at the same time bonding the composite carbon particles together, and for bonding the third material carbon, if present.
Types of binders include polychloroprene, a styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE), and polyvinylidene fluoride (PVDF). An addition amount of the binder is typically in the range of 2 to 30 parts by weight relative to 100 parts by weight of the first carbon material. If the amount of binder is less than 2 parts by weight, the advantages of the binding effect may not be achieved, and if the amount of the binder exceeds 30 parts by weight, the binding effect may become saturated. Generally, the amount of the binder in the coating layer is preferably 5 to 15 parts by weight.
For the application of the carbon mixture in the form of a paste to the electrode plate, a thickener is typically added to the carbon mixture. When an aqueous carbon mixture paste is formed, a cellulose derivative such as CMC and MC, a polyacrylic acid salt, polyvinyl alcohol, or the like is preferred as a thickener. When an organic carbon mixture slurry is formed, N-methyl-2-pyrrolidone (NMP) or the like is preferable as a thickener. When the amount of thickener to be used is more than 20 parts per
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31/50 weight in terms of dry weight in relation to 100% by weight of the first capacitor carbon material, the resulting carbon mixture covering layer may be weak in electrical conductivity and therefore the amount of the thickener is preferably 20% by weight or less.
A short fiber reinforcement material can be added to the carbon mixture. The short fiber reinforcement material is selected to be stable in sulfuric acid and can be selected from at least one of carbon, glass, polyester or the like. The short fiber reinforcement material can have a diameter of 20 pm or less and a length of 0.1 mm to 4 mm. As for the amount of addition of a short fiber reinforcement material, if it is more than 20 parts by weight in relation to 100 parts by weight of the first carbon material, the carbon mixture resulting from the coating layer may have low electrical conductivity and therefore, the amount of addition of the short fiber reinforcing material is preferably 20 parts by weight or less.
A hybrid electrode plate can be produced in such a way that composite carbon particles are prepared by mixing the first carbon material and the second carbon material in the amounts mentioned above and combining them with each other, which can be mixed with 2 to 30 parts by weight of a binder and an adequate amount of a dispersion medium to prepare a mixture of carbon in a paste form and the carbon mixture paste can be applied to the surface of a negative or positive electrode plate ( which normally already contains the active battery material, which is
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Then dried to form a coating layer of porous carbon mixture. It is preferable that 1 to 15% by weight of the carbon mixture is added in relation to the weight of an active material present in the negative or positive plate. If the amount of carbon in the mixture is less than 1% by weight, the advantages may not be obtained, and if the amount exceeds 15% by weight, the resulting coating layer may be too thick and may cause polarization. The amount of the carbon mixture is preferably in the range of 3 to 10% by weight.
The thickness of the coating layer (comprising the composite carbon particles containing carbon mixture) on an electrode can typically be in the range of 0.1 to 0.5 mm. In one embodiment, the coating thickness is provided in a range of 0.05 to 2 mm, 0.08 to 1 mm, or 0.1 to 0.5 mm or about 0.2 mm.
The carbon mixture coating layer can be supplied to one or both surfaces of an electrode.
Electrical Storage Devices
It will be appreciated that an electrical storage device includes at least one pair of positive and negative electrodes, wherein at least one electrode is an electrode according to the present invention.
The electrical storage device, for example, a lead acid battery, is usually mounted with an anode and a cathode (or negative and positive electrode). The electrodes are usually formed from metal current collectors coated with active battery material. In relation to lead acid batteries, the device would normally comprise at least one positive electrode
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33/50 based on lead dioxide, a non-conductive porous separator and at least one negative electrode based on sponge lead coupled together in an electrolyte solution containing sulfuric acid. The electrical storage device may be a regulated valve device.
Electrodes generally comprise a current collector (typically, a grid or plate) with an active battery material applied to it. The active battery material is most commonly applied in paste form to a region of the current collector. The paste may contain additives or materials other than the active battery material. The electrode can be of any suitable shape, although it is typically in the form of a flat plate (grid), or a coiled spiral plate for prismatic cells or coiled spiral. For simplicity of design, flat grids or plates are generally preferred. Current collectors generally provide the base structure of an electrode, and are typically formed from electrically conductive metals, for example, a lead alloy is generally used as a current collector in lead acid batteries. In addition, the materials used for the current collector must be stable in the electrolyte environment.
The term active battery material, or similar term, refers to the ability of a material to receive, store and supply a source of electrical charge and includes battery electrode materials capable of storing electrochemically energy. For example, for a lead acid battery, sponge lead can be used
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34/50 as a negative electrode material and lead dioxide can be used as a positive electrode material. It will be appreciated that the active battery materials can become activated after they have been applied to an electrode or placed within a battery system.
The electrical storage device may comprise one or more negative electrodes, positive electrodes, or a pair of positive and negative electrodes, as described herein. The electrodes and their materials must also have access to an electrolyte that can supply counterions and complete the electrical circuit of the energy storage cell. Chemical compatibility must also be considered, for example, if the two materials share a common electrolyte, both must be stable in that electrolyte.
The active battery material or coating layer comprising the composite carbon particles is typically arranged in the same current collector to be in electrical contact. Examples of this arrangement include: double-sided, layered, tiled, or coated.
In one embodiment, the positive electrode is a positive lead dioxide electrode and the negative electrode is a negative sponge lead electrode. The electrolyte is preferably a sulfuric acid electrolyte solution. In a preferred embodiment, the coating layer of the composite carbon particles is provided on at least a portion of the negative electrode.
In another particular embodiment, an electrical storage device is provided comprising at least one positive electrode based on lead dioxide and at least
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35/50 minus a negative lead-based sponge lead in a sulfuric acid electrolyte solution, where the negative electrode comprises:
a current collector, a first layer deposited on the current collector, the first layer comprising an active sponge lead battery material;
a second layer in contact with at least a portion of the first layer, the second layer comprising composite carbon particles, wherein each of the composite carbon particles comprises a particle of a first capacitor carbon material coated with particles of a second carbon material. electrically conductive carbon.
In addition to the above embodiment, contacting the second layer with at least a portion of the first layer may comprise the second layer covering the first layer. It will be appreciated that the advantages can be obtained by other mechanisms.
The electrical storage device typically further comprises a porous non-conductive separator that separates at least one positive lead-based dioxide electrode and at least one negative lead-based sponge electrode.
The above modalities of electrical storage devices can reduce or suppress sulfation problems in devices with such problems, for example, high performance lead acid batteries operated under high rate partial charge state. In one embodiment, the use of storage devices is provided
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36/50 electric according to the modalities described here under conditions of partial charge state (PSoC) in the range of about 20 to 100% (for example typical for electric vehicles), in the range of about 40 to 60% (for example typical example for hybrid electric vehicles), or in the range of about 70 to 90% (for example typical for light hybrid electric vehicles).
Electrolyte
In the case of lead acid batteries, any suitable acid electrolyte can be used. In the case of lead acid batteries, the electrolyte is typically a sulfuric acid electrolyte.
Busbars or conductors
The bus of a lead acid battery can be of any suitable construction, and can be made of any suitable conductive material, known in the art.
Other battery features
Generally, the battery components will be contained within a battery box with characteristics appropriate for the type of battery used. For example, in the case of lead acid batteries, the lead acid battery can be either from a flooded electrolyte design or a regulated valve design. Where the lead acid battery is a regulated valve lead acid battery, the battery can be of any suitable design, and may, for example, contain electrolyte gel. Specific characteristics of the battery unit suitable for such designs are well known in the art of the invention.
The pressure that can be applied to the lead acid battery can be in the range of 5 to 20 kPa for design
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37/50 flooded with electrolyte, and 20 to 80 kPa for regulated valve lead acid battery design.
Tabs
Generally, each positive and negative electrode is separated from adjacent electrodes by porous separators. The separators maintain an adequate separation distance between adjacent electrodes. The separators located between the immediately adjacent lead-based negative electrodes and lead-dioxide-based positive electrodes can be made of any suitable porous material commonly used in the art, such as porous polymer materials or absorbent glass microfibers (AGM). The separation distance (corresponding to the thickness of the separator) is generally 1 to
2.5 mm for these separators. Suitable polymer materials useful for forming the separators between the positive and negative electrodes that form the battery part are polyethylene and AGM. Polyethylene separators are suitably between 1 and 1.5 mm thick, while AGM separators are suitably between 1.2 and 2.5 mm thick.
Formation of lead acid batteries
After assembling the appropriate components together in a battery case, the lead acid battery usually needs to be formed. The training operation is well known in the field. It is to be understood that references to lead-based and lead-dioxide-based materials are used to refer to lead or lead dioxide itself, materials that contain the metal / metal dioxide or to materials that are converted to
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38/50 lead or lead dioxide, as the case may be, in the given electrode.
As indicated by the language used above, the lead acid battery contains at least one of each type of electrode. The number of individual cells (made up of a positive and negative plate) in the battery depends on the desired voltage of each battery. For a 36-volt battery suitable for use as a light hybrid electric vehicle battery (which can be charged up to 42 volts), this would involve using 18 cells.
Electrode array
Generally, the positive and negative electrodes are interspersed, so that each positive electrode has a negative electrode next to it. However, it will be appreciated that other electrode arrangements can be used depending on the application in question.
Particular additives for electrodes
If there is a difference in the potential window or operational range of potential for one of the electrodes,
gasification of hydrogen and / or oxygen can to occur. For suppress gasification of hydrogen, the electrodes can include an additive or a mix additive that
it comprises an oxide, hydroxide or sulfate of lead, zinc, cadmium, silver, bismuth, or a mixture of these. Generally, it is preferred that the additive comprises at least one lead or zinc oxide, hydroxide or sulfate. For convenience, the additive is suitably one or more oxides selected from lead oxide, zinc oxide, cadmium oxide, silver oxide and bismuth oxide.
It will be appreciated by people skilled in the art who can
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39/50 numerous variations and / or modifications to the invention can be made as shown in the specific embodiments, without departing from the spirit or scope of the invention as widely described. The present modalities should therefore be considered in all respects as illustrative and not restrictive.
It is to be understood that, if any prior art publication is referred to here, such reference does not constitute an admission that the publication is part of the common general knowledge in art, in Australia or in any other country.
In the claims that follow and in the previous description of the invention, except where the context requires otherwise due to the necessary implication or language of expression, the word comprises or variations such as understand or understand is used in an inclusive sense, that is, to specify the presence of indicated features, but does not prevent the presence or addition of other features in various embodiments of the invention.
The present invention will be described in more detail with reference to the Examples and Examples of comparison as follows.
Example 1
Composite carbon particles were produced as follows. 100 parts by weight of activated carbon with an average particle size of 8 pm as a first capacitor carbon material (see Figure 1 (a)) and 60 parts by weight of acetylene black with an average particle size of 0, 1 pm as a second electrically conductive carbon material (see Figure 1 (b)) were ground into
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40/50 set by means of a granule crusher with an average diameter of 5 mm for one hour to obtain composite carbon particles, each comprising the particle of the activated carbon of which the surface is covered and combined with the fine particles of black acetylene (see Figure 2 (a)). The hybrid or composite carbon particles thus obtained were added with SBR as a binder, CMC as a thickener, polyethylene terephthalate (PET) as a short fiber reinforcement material, and water as a dispersion medium, and were then mixed using a mixer, to prepare a carbon mixture paste. The mixed composition of the carbon mixture paste is shown in Table 1.
On the other hand, positive plates and negative plates for use in a regulated valve lead acid storage battery were produced by a known method, and were then subjected to a tank formation treatment, and a series of respective positive plates were prepared. and negative.
With respect to each of the negative plates, the carbon mixture paste prepared above was applied uniformly over the entire surface of the negative active battery material that was previously applied to the plate current collector, which was then dried at 60 ° C for one hour, so that a hybrid negative plate in which a layer of porous carbon mixture coating with a porosity of 75% formed on both surfaces of the negative plate was produced. It has been shown that the advantages provided by the hybrid negative plate thus produced are that the mixing coating layer
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41/50 porous carbon has a thickness of 0.2 mm over a surface, and its weight is 5% by weight in relation to the weight of the active anode material.
Table 1: Mixed composition of carbon mixture paste in Example 1
Composite carbon particles comprisingFirst carbon material: 100 parts by weight of activated carbon particles andSecond carbon material: 60 parts by weight of acetylene black particles Binder SBR 20 parts by weight Thickener CMC 10 parts by weight Short fiber reinforcement PET 13 parts by weight Dispersion medium Water 700 parts by weight
Then, 5 sheets of the hybrid negative plates produced above and 4 sheets of the positive plates were stacked alternately through AGM (Absorbed Glass Mat) separators to mount an element, and 10 using the element, a cell lead acid storage battery. of 2V having a rate capacity of 5 hours of Ah under positive capacity control was produced by a known method, so that a regulated valve lead acid storage battery was produced. In the course of its production, a spacer was placed respectively between the two ends of the element and a battery container so that the degree of compression of the element can be 50 kPa, after the element has been contained in the container. As a solution
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42/50 electrolytic sulfuric acid, 130 ml of an aqueous solution of sulfuric acid having a specific gravity of 1.30 and having dissolved in it 30 g / l of an aluminum sulfate octodecahydrate was poured into the cell. Then, for cell activation, the charging operation was conducted at 1 A for 15 hours, and the discharge operation was conducted at 2 A until the cell voltage reached 1.75 V, and again the charging operation was conducted at 1 A for 15 hours, and the discharge operation was conducted at 2 A until the voltage that the cell reached became 1.75 V, and when a 5 hour rate capacity of the resulting cell was measured, it was 10 Ah.
Example 2
A hybrid negative plate was produced in the same way as in Example 1 except that a carbon mixture paste having the composition mixed as shown in Table 2 below, which was prepared by adding acetylene black with excellent electrical conductivity as a third material of carbon for the carbon mixture paste in Example 1, was used. Using the hybrid negative plate thus produced, a 2V cell lead acid storage battery having a 5-hour rate capacity of 10 Ah, was produced in the same way as in Example 1.
Table 2: Mixed composition of carbon mixture paste in Example 2
Composite carbon particles First carbon material: activated carbon particles and Second carbon material:
understanding
100 parts by weight parts by weight
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43/50
acetylene black particles Third carbon material 20 parts by weight of acetylene black particles Binder SBR 20 parts by weight Thickener CMC 10 parts by weight Short fiber reinforcement material PET 13 parts by weight Dispersion medium Water 700 parts by weight
Example 3
A hybrid negative plate was produced in the same way as in Example 2 with the exception that a carbon mixture paste was used with the mixed composition as shown in Table 3 below, where 20 parts by weight of a steam growth nanocarbon fiber (VGCF) were used as the third carbon material instead of 20 parts by weight of the acetylene black particles. Using the hybrid negative plate thus produced, a 2V cell lead acid storage battery having a 5 hour rate capacity of 10 Ah, was produced in the same way as in Example 1.
Table 3: Mixed composition of carbon mixture paste in Example 3
Composite carbon particles
First carbon material: 100 parts by weight of activated carbon particles and
Second carbon material: 60 parts by weight of acetylene black particles
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44/50
Third carbon material VGCF 20 parts by weight Binder SBR 20 parts by weight Thickener CMC 10 parts by weight Short fiber reinforcement material PET 13 parts by weight Dispersion medium Water 700 parts by weight
Comparison example 1
A hybrid negative plate was produced in the same way as in Example 1 using a carbon mixture paste having the composition mixed as shown in the following Table 4 having the same composition mixed as in Table 1, except that the mixed powders used were prepared by simply mixing 100 parts by weight of the activated carbon particles as the first carbon material and 60 parts by weight of the 10 acetylene black particles as the second carbon material (see Figure 2 (b)), without combining them in together in a compound (see Figure 2 (a)). Using the hybrid negative plate thus produced, a 2V cell lead acid storage battery having a 5 hour charge capacity of 10 15 Ah, was produced in the same way as in Example 1.
Table 4: Mixed composition of carbon mixture paste in Comparison example 1
Mixed powder
First material carbon: 100 parts per Weight in carbon particles activated andSecond material carbon: 60 parts per Weight in
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45/50
acetylene black particles Binder SBR 20 parts by weight Thickener CMC 10 parts by weight Short fiber reinforcement material PET 13 parts by weight Dispersion medium Water 700 parts by weight
Comparison Example 2
A 2V cell lead acid accumulation battery having a 5-hour rate capacity of 10 Ah, was produced in the same way as in Example 1, except that an element was assembled from 5 sheets of the negative plates which are the same as in Example 1 and which are not yet applied with the carbon mixture paste, and 4 sheets of the positive plates and separators which are the same as in Example 1.
Life test
With respect to each lead acid battery in Examples 1 to 3 and the lead acid batteries in Comparison Examples 1 and 2 as produced above, a life test was conducted by repeating a quick charge / discharge operation on the PSOC based on the simulation of driving a HEV. Specifically, each storage battery was discharged at 2 A for one hour so that the SOC was made 80%, and subsequently the discharge operation at 50 A for one second and the charging operation at 20 A for one second was repeated 500 times, and then the charging operation at 30 A for one second and a one second pause period was repeated
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46/50
510 times. This was considered as a cycle. This cycle was repeated, and a time point when the battery discharge voltage reached 0 V was determined to be a lifetime. The results are shown in Table 5 below.
Table 5: Results of the life test
Example 1 1060 cycles Example 2 1130 cycles Example 3 1210 cycles Comparison example 1 820 cycles Comparison example 2 180 cycles
From Table 5 above, it is evident that the lead acid batteries, respectively supplied with the hybrid negative plates of the invention described in Examples 1, 2 and 3, are individually remarkably improved in the life cycle, compared to the storage battery lead acid battery supplied with the conventional hybrid negative plate described in Comparison Example 1 or the lead acid storage battery supplied with the common negative plate described in Comparison Example 2.
Example 4
Then, using the carbon mixture paste from Table 1 and the negative plates each having a width of 102 mm, with a total height of 108.5 mm and a thickness of
1.5 mm, a series of hybrid negative plates were produced in the same way as in Example 1. On the other hand, each having a width of 102 mm, with a height of
107.5 mm and a thickness of 1.7 mm, a series of positive plates were produced.
With regard to a flooded type lead acid storage battery of a size B24 according to
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47/50
JIS D 5301, which has a width of 126 mm, a length of 236 mm and a height of 200 mm and comprises 6 cells of an assembled element by alternatively stacking 7 sheets of the aforementioned hybrid negative plates and 6 sheets of the aforementioned positive plates using 1.0 mm thick laminated separators made of laminated glass fiber non-woven fabric on the polyethylene surface, it was contained in each battery cell chamber by means of spacers, in the same way as in Example 1 of so that element compression was done 20 kPa. Then the cells were connected in series according to a common method and a cap was placed on it, and then 450 ml of an electrolytic solution of sulfuric acid was poured over each of the cell chambers and then adjusted so that the specific gravity of the electrolyte solution became 1.285 after the vessel was formed, so that a flooded type lead acid storage battery with a 5-hour rate capacity of 42 Ah was produced.
Using the flooded lead acid storage battery thus produced, a life test was carried out at an ambient temperature of 25 ° C under the following conditions for an idle-stop system vehicle. That is, the discharge operation was conducted at 45 A for 59 seconds and subsequently the discharge operation was conducted at 300 A for one second, and then the charging operation at a constant voltage of 14.0 V was conducted at 100 A for 60 seconds. The cycle of loading and unloading operations mentioned above was repeated 3600 times, and subsequently, the resulting battery was left in
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48/50 rest for 48 hours, and the aforementioned loading and unloading operations were repeated once again. A time point when the storage battery voltage became 7.2 V was determined to be its life, and the number of cycles at which time was determined to be a life cycle. The result is shown in Table 6 below.
Table 6: Results of the life test
Example 4 85000 cycles Example 5 88000 cycles Example 6 90000 cycles Comparison example 3 75000 cycles Comparison example 4 35000 cycles
Example 5
A series of hybrid negative plates were produced in the same way as in Example 4, except that the carbon paste mixture as shown in Table 2 was used. Using these hybrid negative plates, a flooded lead acid storage battery having a 5-hour rate capacity of 42 Ah was produced in the same manner as in Example 4.
Using this battery, a life cycle test was conducted in the same way as in Example 4. The result is shown in Table 6.
Example 6
A series of hybrid negative plates were produced in the same way as in Example 4, except that a mixture of a carbon paste as shown in Table 3 was used. Using these hybrid negative plates, a flooded lead acid storage battery having a 5-hour rate capacity of 42 Ah was
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49/50 produced in the same way as in Example 4.
Using this battery, a life cycle test was conducted in the same way as in Example 4. The result is shown in Table 6.
Comparison example 3
A series of hybrid negative plates were produced in the same way as in Example 4, except that the conventional carbon blend paste as shown in Table 4 was used. Using these hybrid negative plates, a flooded lead acid storage battery having a 5-hour rate capacity of 42 Ah was produced in the same way as in Example 4.
Using this battery, a life cycle test was conducted in the same way as in Example 4. The result is shown in Table 6.
Comparison example 4
Using the negative plates described in Example 4, each of which has no carbon mixture paste applied, a flooded type lead acid storage battery with a 5 Ah rate capacity of 42 Ah was produced in the same way as in Example 4 Using this battery, a life cycle test was conducted in the same way as in Example 4. The result is shown in Table 6.
As can be seen from Table 6, the flooded lead acid storage batteries respectively supplied with the hybrid negative plates described in Examples 4, 5 and 6 are individually noticeably improved in the life cycle when compared to the battery. flooded lead acid storage provided with hybrid negative plate
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Conventional 50/50 described in Comparison Example 3 and the flooded lead acid storage battery provided with the common negative plate described in Comparative Example 4.

权利要求:
Claims (6)
[1]
1. Electrode comprising an active battery material for a lead acid storage battery, wherein the electrode surface is provided with a coating layer comprising a carbon mixture containing composite carbon particles, wherein each of the composite carbon particles comprises a particle of a first capacitor carbon material with particles of a second electrically conductive carbon material characterized by the fact that particles of a second electrically conductive carbon material are adhered to a surface of the first capacitor carbon material, in that the surface coverage on the particles of the first capacitor carbon material by the second electrically conductive carbon material is at least 20%.
[2]
2. Electrode according to claim 1, characterized by the fact that the surface coverage on the particles of the first capacitor carbon material by the second electrically conductive carbon material is at least 50%.
[3]
Electrode according to either claim 1 or claim 2, characterized in that the particle size of the second electrically conductive carbon material is one fifth or less than that of the first capacitor carbon material.
[4]
4. Electrode according to claim 3, characterized by the fact that the particle size of the second electrically conductive carbon material is one tenth or less than that of the first carbon material of
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2/6 capacitor.
5. Electrode, in a deal with any one of claims 1 to 4, featured by the fact that the proportion of the weight O, % of the first carbon material capacitor for the second material carbon electrically conductive its between 15: : 1 to 10: 8.6. Electrode, in a deal with any one of claims 1 to 5, featured by the fact that the
first capacitor carbon material has a specific surface area of at least 500 m ² / g, measured by adsorption using BET isotherm.
7. Electrode according to claim 6, characterized by the fact that the specific surface area is at least 1000 m ² / g.
8. Electrode according to any of claims 1 to 7, characterized by the fact that the first capacitor carbon material is selected from activated carbon.
Electrode according to any one of claims 1 to 8, characterized in that the second electrically conductive carbon material is a high electrically conductive carbonaceous material having a measured conductivity of at least 0.6 Scm ^-1 at 500 kPa at 20 ° C.
An electrode according to any one of claims 1 to 9, characterized in that the second electrically conductive carbon material is selected from at least one carbon black, graphite, glassy carbon, and a nanocarbon fiber.
11. Electrode, according to any of the
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3/6 claims 1 to 10, characterized in that the carbon mixture comprises a third electrically conductive carbon material.
12. Electrode according to claim 11, characterized by the fact that the third electrically conductive carbon material is selected from at least one of a carbon black, graphite, glassy carbon, and a nanocarbon fiber.
13. Electrode according to claim 12, characterized by the fact that the nanocarbon fiber is selected from at least one carbon nanowire, a carbon nanotube, and a carbon trizel.
Electrode according to any one of claims 1 to 13, characterized in that the coating layer of the carbon mixture comprises 4 to 100 parts by weight of the second electrically conductive carbon material in relation to 100 parts by weight of the first capacitor carbon material.
15. Electrode according to claim 14, characterized in that the coating layer of the carbon mixture further comprises 50 parts by weight or less of the third electrically conductive carbon material in relation to 100 parts by weight of the first carbon material capacitor carbon.
Electrode according to any one of claims 1 to 15, characterized in that the coating layer of the carbon mixture comprises 2 to 30 parts by weight of a binder in relation to 100 parts by weight of the first carbon material capacitor.
Petition 870190077983, of 12/08/2019, p. 66/70
4/6
17. Electrode according to any one of claims 1 to 13, characterized in that the coating layer of the carbon mixture comprises 4 to 100 parts by weight of the second electrically conductive carbon material in relation to 100 parts by weight of the first capacitor carbon material, 50 parts by weight or less of the third electrically conductive carbon material, 2 to 30 parts by weight of a binder, 20 parts by weight or less of a thickener, and 20 parts by weight or less than one short fiber relative to 100 parts by weight of the first capacitor carbon material.
18. Electrode according to any one of claims 1 to 17, characterized in that an amount of the carbon mixture for the electrode coating layer is 1 to 15% by weight in relation to the weight of the active battery material on the electrode.
19. Electrode according to any one of claims 1 to 18, characterized in that the electrode is a negative electrode comprising negative active battery material for a lead acid storage battery.
20. Electrode according to any of claims 1 to 18, characterized in that the electrode is a positive electrode comprising positive active battery material for a lead acid storage battery.
21. Electrode according to any one of claims 1 to 20, characterized by the fact that the carbon mixture containing composite carbon particles is produced by at least one of grinding, granulating and
Petition 870190077983, of 12/08/2019, p. 67/70
[5]
5/6 unification, the particles of the first capacitor carbon material with particles of the second electrically conductive carbon material.
22. Electrode according to claim 21, characterized by the fact that the grinding is ball or granule grinding.
23. Electrical storage device for a lead acid based system, characterized in that it comprises the electrode as defined in any one of claims 1 to 22.
24. Electrical storage device according to claim 23, characterized in that the device is a lead acid storage battery.
25. Electrical storage device comprising at least one positive electrode based on lead dioxide and at least one negative electrode based on sponge lead in a solution of sulfuric acid electrolyte, wherein the negative electrode comprises:
a current collector;
a first layer deposited on the current collector, the first layer comprising an active battery material of sponge lead;
a second layer in contact with at least a portion of the first layer, the second layer comprising composite carbon particles, wherein each of the composite carbon particles comprises a particle of a first capacitor carbon material with particles of a second carbon material electrically conductive, characterized by the fact that particles of the second electrically conductive carbon material are adhered to
Petition 870190077983, of 12/08/2019, p. 68/70
[6]
6/6 a surface of the first capacitor carbon material, wherein the surface coverage on the particles of the first capacitor carbon material by the second electrically conductive carbon material is at least 5 20%.

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同族专利:

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公开号 | 公开日

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WO2012083358A1|2012-06-28|

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AU2011349121B2|2014-05-15|

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CN103493267B|2017-05-24|

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AU2011349121A1|2013-05-02|

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MY177214A|2020-09-09|

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JP2012133959A|2012-07-12|

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RU2585240C2|2016-05-27|

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JP2014505968A|2014-03-06|

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JP5771701B2|2015-09-02|

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US9812703B2|2017-11-07|

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CN103493267A|2014-01-01|

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CA2822468A1|2012-06-28|

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MX2013007016A|2014-01-20|

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US20140127565A1|2014-05-08|

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ES2649590T3|2018-01-12|

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RU2013133628A|2015-01-27|

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PL2656420T3|2018-04-30|

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KR20140025331A|2014-03-04|

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EP2656420B1|2017-09-13|

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EP2656420A1|2013-10-30|

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EP2656420A4|2015-12-23|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-06-11| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-12-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-01-28| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2010284040A|JP2012133959A|2010-12-21|2010-12-21|Composite capacitor negative electrode plate for lead storage battery, and lead storage battery|

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PCT/AU2011/001647|WO2012083358A1|2010-12-21|2011-12-21|Electrode and electrical storage device for lead-acid system|

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