CN110993896B - Lead-carbon battery negative electrode lead paste and preparation method thereof - Google Patents
Lead-carbon battery negative electrode lead paste and preparation method thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M10/06—Lead-acid accumulators
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The lead-carbon battery negative lead plaster comprises the following components in parts by weight: 100-105 parts of lead powder, 7-15 parts of ordered mesoporous carbon pulp, 0.08-0.12 part of binder, 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate, 0.08-0.13 part of hydrogen inhibitor and 10-14 parts of sulfuric acid; wherein the ordered mesoporous carbon slurry comprises hydrogen peroxide, ordered mesoporous carbon and ozone water. According to the lead-carbon battery cathode lead plaster, the ordered mesoporous carbon slurry is added, and the ordered mesoporous carbon has a larger specific area and better hydrophilicity and can be better contacted with an electrolyte. Meanwhile, sodium lignosulfonate capable of inhibiting sulfation is added, so that the service life of the lead-carbon battery can be prolonged, and the cycle time is longer.
Description
Technical Field
The invention relates to the technical field of lead-carbon batteries, in particular to a lead paste for a negative electrode of a lead-carbon battery and a preparation method thereof.
Background
The lead-carbon battery is a capacitive lead-acid battery, is evolved from the traditional lead-acid battery, and is characterized in that activated carbon is added into the negative electrode of the lead-acid battery so as to solve the problem of short cycle life of the traditional lead-acid battery and obviously improve the service life of the lead-acid battery.
However, the problem of limited sulfation still remains in the industry how to further reduce the effect of sulfation to improve the service life of the lead-carbon battery.
Disclosure of Invention
Therefore, the lead-carbon battery negative electrode lead paste and the preparation method thereof are needed to improve the service life of the lead-carbon battery.
The lead-carbon battery negative electrode lead paste comprises the following components in parts by mass:
100-105 parts of lead powder, 7-15 parts of ordered mesoporous carbon pulp, 0.08-0.12 part of binder, 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate, 0.08-0.13 part of hydrogen inhibitor and 10-14 parts of sulfuric acid; the ordered mesoporous carbon-carbon slurry comprises hydrogen peroxide, ordered mesoporous carbon and ozone water, wherein the mass ratio of the hydrogen peroxide to the ordered mesoporous carbon to the ozone water is 80-100: 1: "10-12".
In one embodiment, the binder is a short fiber.
In one embodiment, the binder is water-soluble carboxymethyl cellulose, polyvinyl alcohol, starch, or dextrin.
In one embodiment, the density of the sulfuric acid is 1.325 g/ml.
In one embodiment, the hydrogen suppressing agent is indium oxide.
In one embodiment, the hydrogen peroxide solution is a hydrogen peroxide solution with a mass fraction of 10%.
In one embodiment, the preparation method of the ordered mesoporous carbon-carbon slurry comprises the following steps:
mixing ozone water, hydrogen peroxide and ordered mesoporous carbon, and reacting for 2-2.5 hours at 60-68 ℃ to prepare the ordered mesoporous carbon slurry.
In one embodiment, the concentration of ozone in the ozone water is 7mg/L-12 mg/L.
A preparation method of lead-carbon battery negative electrode lead paste is the lead-carbon battery negative electrode lead paste in any one of the embodiments, and comprises the following steps:
mixing and stirring lead powder, the ordered mesoporous carbon slurry, the binder, sodium lignosulfonate, humic acid, barium sulfate and a hydrogen inhibitor, adding sulfuric acid, and mechanically stirring and mixing to obtain the lead-carbon battery cathode lead paste.
In one embodiment, the lead powder, the ordered mesoporous carbon-carbon slurry, the binder, the sodium lignosulfonate, the humic acid, the barium sulfate and the hydrogen inhibitor are mixed and stirred, the lead powder and the ordered mesoporous carbon-carbon slurry are firstly mixed and uniformly dispersed, and then the binder, the sodium lignosulfonate, the humic acid, the barium sulfate and the hydrogen inhibitor are added.
According to the lead-carbon battery cathode lead plaster, the ordered mesoporous carbon slurry is added, so that the ordered mesoporous carbon has a larger specific area and better hydrophilicity, and can be better contacted with an electrolyte. Meanwhile, sodium lignosulfonate capable of inhibiting sulfation is added, so that the service life of the lead-carbon battery can be prolonged, and the cycle time is longer. By adding humic acid, barium sulfate and a hydrogen inhibitor, the service life of the lead-carbon battery can be further prolonged, the battery capacity of the lead-carbon battery can be improved, and the lead-carbon battery has good application potential.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. Preferred embodiments of the present invention are given. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. 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. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, the lead-carbon battery negative electrode lead paste comprises the following components in parts by mass: 100-105 parts of lead powder, 7-15 parts of ordered mesoporous carbon pulp, 0.08-0.12 part of binder, 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate, 0.08-0.13 part of hydrogen inhibitor and 10-14 parts of sulfuric acid; the ordered mesoporous carbon-carbon slurry comprises hydrogen peroxide, ordered mesoporous carbon and ozone water, wherein the mass ratio of the hydrogen peroxide to the ordered mesoporous carbon to the ozone water is 80-100: 1: "10-12". For another example, lead paste for the negative electrode of a lead-carbon battery is abbreviated as lead paste, or negative lead paste. For another example, the negative electrode lead paste is a lead-carbon battery negative electrode lead paste or a hydrogen-suppressing negative electrode lead paste of a lead-carbon battery.
In order to further explain the negative lead plaster of the lead-carbon battery, the application firstly provides a negative lead plaster applied to the lead-carbon battery, which comprises lead powder, an activated carbon material, a binder, sodium lignosulfonate, humic acid, barium sulfate, a hydrogen inhibitor and sulfuric acid.
In the embodiment, the sodium lignosulfonate is added to the negative lead paste of the negative material, so that the low-temperature discharge capacity of the battery can be improved, the cycle life of the battery can be prolonged, and particularly, the sodium lignosulfonate can prevent the precipitation of lead sulfate (PbSO)4) And the passivation layer can reduce the influence of sulfation, thereby prolonging the service life of the lead-carbon battery.
In the embodiment, the humic acid is added into the negative lead plaster, so that the discharge capacity of the battery can be improved, and the expansion and contraction of the active substances on the polar plate can be improved to a certain extent.
In the embodiment, barium sulfate is added into the negative lead paste, so that the effect of lead specific surface area shrinkage can be prevented, the better specific surface area of the surface of the electrode material is kept, the barium sulfate has a lattice parameter similar to that of lead sulfate, is an isomorphous substance, and is highly dispersed in the negative active material and can be used as the crystal center of the lead sulfate during discharging; since lead sulfate can be crystallized and precipitated on the isomorphous barium sulfate, lead sulfate crystal nuclei do not need to be formed, and thus supersaturation necessary for forming the crystal nuclei is not generated. PbSO produced under conditions of low supersaturation4Is relatively loose and porous and is beneficial to H2SO4The diffusion of (2) reduces concentration polarization; the presence of barium sulfate leads to a product of PbSO4Not precipitated on lead, butPrecipitating on barium sulfate so that the active substance lead is not PbSO4The passivation layer is covered, and the barium sulfate plays a role in delaying passivation. Therefore, the cycle service life of the battery can be prolonged by adding barium sulfate, and the discharge capacity of the battery is maintained to a certain extent.
In the embodiment, the hydrogen evolution inhibiting effect is achieved by adding the hydrogen inhibitor, so that the discharge capacity of the battery is further improved. For example, the hydrogen suppressing agent includes, but is not limited to, at least one of indium oxide, bismuth oxide, and gallium oxide.
In the embodiment, the adhesive is added to achieve a good adhesive effect. For example, the binder includes, but is not limited to, at least one of water-soluble carboxymethyl cellulose, polyvinyl alcohol, starch, dextrin, and short fibers. For another example, the binder is short fibers, and for another example, the short fibers are polyester fibers, so that a better binding effect can be achieved.
The density of the sulfuric acid in this example was 1.1g/ml to 1.4 g/ml. Preferably, the density of the sulfuric acid is 1.325 g/ml.
The activated carbon material in this embodiment may be a carbon material on an existing lead-carbon battery, or may be a carbon material introduced later in this application. By adding the activated carbon material into the lead-acid battery, the specific surface area of the negative active material can be better increased due to the porous structure of the activated carbon, so that the electrolyte can better permeate into the material to participate in the reaction, and the carbon can enhance the conductivity of the negative electrode and can be used as a reaction site and a crystallization site for converting lead sulfate precipitation salt into metallic lead to a certain extent. In addition, certain electrolyte can be stored in the carbon with a porous structure, the charging efficiency can be improved in the charging process, and the capacitance of the carbon can be used as a buffer of the battery during discharging to protect the battery from being damaged by discharging.
The lead-carbon battery cathode lead plaster comprises lead powder, an active carbon material, a binder, sodium lignosulfonate, humic acid, barium sulfate, a hydrogen inhibitor and sulfuric acid, wherein the sodium lignosulfonate, the humic acid, the barium sulfate, the hydrogen inhibitor and the active carbon material jointly act, so that the discharge capacity of a battery is improved, and the cycle service life of the battery is prolonged.
In one embodiment, the components of the lead paste for the negative electrode of the lead-carbon battery comprise the following components in parts by mass: the lead powder comprises, by weight, 100-105 parts of lead powder, 0.08-0.12 part of a binder, 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate, 0.08-0.13 part of a hydrogen inhibitor and 10-14 parts of sulfuric acid, and thus, through research by the applicant, the use of 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate and 0.08-0.13 part of a hydrogen inhibitor can better improve the discharge capacity and the cycle service life of the battery, and when the number is lower than the range, the influence on the discharge capacity and the cycle service life is relatively limited. In the present application, no parts by mass of the activated carbon material are given because the amount of activated carbon added is generally different for different activated carbons.
In order to further improve the capacity of the lead-carbon battery, the applicant improves an activated carbon material, and in one embodiment, the lead-carbon battery negative electrode lead paste comprises lead powder, ordered mesoporous carbon powder, a binder, sodium lignosulfonate, humic acid, barium sulfate, a hydrogen inhibitor and sulfuric acid, wherein the mass of the ordered mesoporous carbon powder is 0.008 to 0.012 of that of the lead powder. In the embodiment, ordered mesoporous carbon powder is added, the ordered mesoporous carbon has a pore diameter within the range of 2-50nm, is porous inside and penetrates to the outside, is highly ordered and uniform in three-dimensional arrangement and has a relatively uniform pore diameter, and a mutually-communicated pore system is formed, the interaction between mesopores and atoms, ions, molecules and even larger objects is not limited to the outer surface but more importantly penetrates through the inside of the whole material, so that the mesoporous carbon has a huge specific surface area, a uniformly adjustable mesoporous pore diameter and good stability and conductivity, the ordered mesoporous carbon powder is applied to a cathode material of a lead carbon battery, the ordered mesoporous carbon powder is used for replacing a traditional common carbon material, the ordered mesoporous carbon has a larger surface area, the contact area with an electrolyte can be increased, the ordered mesoporous carbon powder is beneficial to adsorbing the electrolyte, and the electrolyte can better penetrate into the material to participate in reaction, and the carbon can enhance the conductivity of the negative electrode and can be used as a reaction site and a crystallization site for converting lead sulfate precipitation salt into metallic lead to a certain extent, so that the specific capacity of the lead-carbon battery can be improved. The ordered mesoporous carbon can also store electrolyte with more capacity, the charging efficiency can be improved in the charging process, and the larger capacitance of the ordered mesoporous carbon can be used as a buffer of the battery during discharging to protect the battery from being damaged by discharging.
In the embodiment, the quality of the ordered mesoporous carbon powder is 0.008 to 0.012 of the quality of the lead powder, and the applicant researches show that when the quality of the ordered mesoporous carbon powder is lower than 0.008 of the quality of the lead powder, the capacity improvement of the ordered mesoporous carbon powder on the lead-carbon battery is limited, and when the quality of the ordered mesoporous carbon powder is higher than 0.012 of the quality of the lead powder, the hydrogen evolution phenomenon easily occurs, and the negative electrode hydrogen evolution is aggravated in the formation or charging process, so that the negative electrode hydrogen evolution aggravates the electrolyte loss, the internal resistance is increased, and the battery failure is accelerated. The applicant researches and discovers that the capacity of the lead-carbon battery can be better improved, the problem of hydrogen evolution of the lead-carbon battery can be solved, the battery can be protected from discharge damage, and the cycle service life of the battery can be prolonged by setting the mass of the ordered mesoporous carbon powder to be 0.008 to 0.012 of the mass of the lead powder. Preferably, the mass of the ordered mesoporous carbon powder is 0.011 of the mass of the lead powder, so that the discharge capacity of the battery can be further improved and the cycle service life of the battery can be further prolonged. For example, the ordered mesoporous carbon has a specific surface area of 500m2/g～1500m2(ii) in terms of/g. For another example, the pore diameter of the ordered mesoporous carbon is 2 nm to 10 nm. For another example, the ordered mesoporous carbon is CMK-3. Therefore, the discharge capacity of the battery can be better improved, and a certain protection effect can be achieved on large-current discharge of the battery.
In another embodiment, the lead-carbon battery negative electrode lead paste comprises the following components in parts by mass: 100-105 parts of lead powder, 0.08-0.12 part of binder, 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate, 0.08-0.09 part of hydrogen inhibitor and 10-14 parts of sulfuric acid; wherein the mass of the ordered mesoporous carbon powder is 0.008 to 0.012 of the mass of the lead powder. Therefore, the lead-carbon battery cathode lead plaster adopts the ordered mesoporous carbon powder to replace the traditional common carbon material, the ordered mesoporous carbon has larger surface area, the contact area with the electrolyte can be increased, the adsorption of the electrolyte is facilitated, and the specific capacity of the lead-carbon battery can be increased. In addition, the addition of the ordered mesoporous carbon can reduce the addition of the carbon.
When the activated carbon material is ordered mesoporous carbon powder, the application continues to provide a preparation method of the lead-carbon battery cathode lead paste, which comprises the following steps: uniformly mixing lead powder, ordered mesoporous carbon powder, a binder, sodium lignosulfonate, humic acid, barium sulfate and a hydrogen inhibitor, adding sulfuric acid, and mechanically stirring and mixing to obtain the lead-carbon battery cathode lead paste. Thus, the lead paste can be prepared well. Preferably, in the preparation process, the lead powder and the ordered mesoporous carbon powder are uniformly mixed, then the sodium lignosulphonate, the humic acid, the barium sulfate and the hydrogen inhibitor are added, and then the sulfuric acid is added. Preferably, in order to further reduce the influence of hydrogen evolution of the battery, in the preparation process, the hydrogen inhibitor is firstly uniformly mixed with the ordered mesoporous carbon powder, then the lead powder is added and uniformly mixed, then the binder, the sodium lignosulfonate, the humic acid and the barium sulfate are added and uniformly mixed, and finally the sulfuric acid is added to prepare the lead-carbon battery cathode lead plaster. According to the carbon battery cathode lead plaster prepared by the preparation method of the lead-carbon battery cathode lead plaster, the conventional common carbon material is replaced by the ordered mesoporous carbon powder, the ordered mesoporous carbon has a larger surface area, the contact area with the electrolyte can be increased, the adsorption of the electrolyte is facilitated, and the specific capacity of the lead-carbon battery can be increased. In addition, the addition of the ordered mesoporous carbon can reduce the addition of the carbon. The above-mentioned negative lead paste for a lead-carbon battery is applied to a negative plate of a lead-carbon battery, please refer to the application of the conventional negative lead paste to the negative plate, for example, the negative lead paste for a lead-carbon battery as described in any of the above embodiments is coated on a negative plate grid.
In order to further improve the contact area between the ordered mesoporous carbon and the electrolyte, the application also carries out hydrophilic modification on the ordered mesoporous carbon in the embodiment so as to improve the contact area between the ordered mesoporous carbon and the electrolyte. The application also provides a lead-carbon battery cathode lead paste prepared from the ordered mesoporous carbon through hydrophilic modification. In one embodiment, the lead-carbon battery negative electrode lead paste comprises the following components in parts by mass: 100-105 parts of lead powder, 7-15 parts of ordered mesoporous carbon pulp, 0.08-0.12 part of binder, 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate, 0.08-0.13 part of hydrogen inhibitor and 10-14 parts of sulfuric acid; the ordered mesoporous carbon-carbon slurry comprises hydrogen peroxide, ordered mesoporous carbon and ozone water, wherein the mass ratio of the hydrogen peroxide to the ordered mesoporous carbon to the ozone water is 80-100: 1: "10-12". In the embodiment, the ordered mesoporous carbon is subjected to hydrophilic modification to form hydrophilicity of the ordered mesoporous carbon, so that the contact area of the ordered mesoporous carbon and the electrolyte is increased, and the purposes of increasing the charge and discharge capacity and prolonging the cycle service life of the battery are achieved. In this embodiment, the ordered mesoporous carbon is subjected to hydrophilic modification by using the ordered mesoporous carbon and the ozone water, and the mass ratio of the hydrogen peroxide to the ordered mesoporous carbon to the ozone water is "80 to 100": 1: the applicant finds that the hydrophilic groups of the ordered mesoporous carbon can be improved better, and 6% of oxygen-containing groups can be introduced into the surface of the ordered mesoporous carbon at most.
It is further noted that, in other fields, the ordered mesoporous carbon is modified by using nitric acid for hydrophilic modification, although the effect of nitric acid modification is good, at most 8% of oxygen-containing groups can be introduced on the surface of the ordered mesoporous carbon, nitric acid is easy to volatilize, the requirement on the operating environment is high, the environment is easy to be polluted, and the environmental protection property is poor. In the literature, hydrogen peroxide is singly used for modifying the ordered mesoporous carbon, and in practical application, at most, 3 percent of oxygen-containing groups can be introduced into the ordered mesoporous carbon and exist in the forms of phenols and hydroquinones. In the present application, the applicant has found that, by adding hydrogen peroxide and ozone water simultaneously, the mass ratio of the hydrogen peroxide to the ordered mesoporous carbon to the ozone water is "80-100": 1: 10-12, so that 6% of oxygen-containing groups can be introduced into the surface of the ordered mesoporous carbon at most, the hydrophilic capability of the ordered mesoporous carbon can be further improved, and the fact that hydrogen peroxide and ozone water have a certain synergistic effect on hydrophilic passivation of the ordered mesoporous carbon is proved. Of course, the mechanism of this concern is yet to be further investigated. According to the lead-carbon battery cathode lead plaster, the ordered mesoporous carbon slurry is added, so that the specific area is large, the ordered mesoporous carbon slurry has good hydrophilicity, the contact area with an electrolyte can be increased, and meanwhile, sodium lignosulfonate capable of inhibiting sulfation is added, so that the service life of a lead-carbon battery can be prolonged, and the cycle time is longer. By adding humic acid, barium sulfate and a hydrogen inhibitor, the service life of the lead-carbon battery can be further prolonged, the battery capacity of the lead-carbon battery can be improved, and the lead-carbon battery has good application potential.
In one embodiment, the hydrogen peroxide solution is a hydrogen peroxide solution with a mass fraction of 10%. For another example, the concentration of ozone in the ozone water is 7mg/L-12 mg/L. Therefore, the surface hydrophilic modification can be better carried out on the ordered mesoporous carbon.
In one embodiment, the specific hydrophilic modification process, or the preparation method of the ordered mesoporous carbon slurry, includes the following steps: mixing ozone water, hydrogen peroxide and ordered mesoporous carbon, and reacting for 2-2.5 hours at 60-68 ℃ to obtain the ordered mesoporous carbon slurry. Therefore, the hydrophilic groups of the ordered mesoporous carbon can be well improved, and 6% of oxygen-containing groups can be introduced into the surface of the ordered mesoporous carbon at most. Preferably, the preparation method of the ordered mesoporous carbon slurry comprises the following steps: mixing ozone water, hydrogen peroxide and ordered mesoporous carbon, and reacting at 68 ℃ for 2-2.5 hours, preferably, the preparation method of the ordered mesoporous carbon slurry comprises the following steps: mixing ozone water, hydrogen peroxide and ordered mesoporous carbon, and reacting for 2.5 hours at 68 ℃, thus better preparing the ordered mesoporous carbon slurry.
In a preferred embodiment, the mass ratio of the hydrogen peroxide to the ordered mesoporous carbon to the ozone water is 80: 1: 10, so that 6 percent of oxygen-containing groups can be well introduced into the surface of the ordered mesoporous carbon at most. The lead paste for the negative electrode of the combined lead-carbon battery comprises the following components in parts by mass: 100-105 parts of lead powder, 7-15 parts of ordered mesoporous carbon pulp, 0.08-0.12 part of binder, 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate, 0.08-0.13 part of hydrogen inhibitor and 10-14 parts of sulfuric acid; the mass of the ordered mesoporous carbon is 0.01099-0.115% of that of the lead powder. Therefore, in the preferred embodiment, the mass of the ordered mesoporous carbon is 0.011% of the mass of the lead powder.
According to the lead-carbon battery cathode lead plaster, the ordered mesoporous carbon slurry is added, so that the specific area is large, and the lignosulphonate capable of inhibiting sulfation is added, so that the service life of the lead-carbon battery can be prolonged, and the cycle time is longer. By adding humic acid, barium sulfate and a hydrogen inhibitor, the service life of the lead-carbon battery can be further prolonged, the battery capacity of the lead-carbon battery can be improved, and the lead-carbon battery has good application potential.
When the ordered mesoporous carbon is subjected to hydrophilic modification, the application continues to provide a preparation method of the lead-carbon battery cathode lead paste, and the preparation method of the lead-carbon battery cathode lead paste comprises the following steps: mixing and stirring lead powder, the ordered mesoporous carbon slurry, the binder, sodium lignosulfonate, humic acid, barium sulfate and a hydrogen inhibitor, adding sulfuric acid, and mechanically stirring and mixing to obtain the lead-carbon battery cathode lead paste. Preferably, during mixing and stirring of the lead powder, the ordered mesoporous carbon-carbon slurry, the binder, the sodium lignosulfonate, the humic acid, the barium sulfate and the hydrogen inhibitor, the lead powder and the ordered mesoporous carbon-carbon slurry are firstly mixed and dispersed uniformly, and then the binder, the sodium lignosulfonate, the humic acid, the barium sulfate and the hydrogen inhibitor are added. The lead-carbon battery cathode lead paste prepared by the preparation method has a large specific area by adding the ordered mesoporous carbon slurry, and the sodium lignosulfonate capable of inhibiting sulfation is added, so that the service life of the lead-carbon battery can be prolonged well, and the cycle time is prolonged. By adding humic acid, barium sulfate and a hydrogen inhibitor, the service life of the lead-carbon battery can be further prolonged, the battery capacity of the lead-carbon battery can be improved, and the lead-carbon battery has good application potential.
The present application also sets out studies from the hydrogen suppressants in an attempt to improve the capacity of lead-carbon batteries. It should be noted that, the capacity of the existing lead-carbon battery still has a great room for improvement, and how to improve the capacity of the lead-carbon battery from the perspective of the hydrogen inhibitor is also a concern in the industry. The existing hydrogen inhibitor is usually added with a single component, such as indium oxide, bismuth oxide or gallium oxide, so as to achieve the effect of inhibiting hydrogen evolution. The applicant continues to improve the hydrogen inhibitor, and thus the present application continues to provide a hydrogen-inhibiting negative electrode lead paste for a lead-carbon battery, which is improved from the perspective of the hydrogen inhibitor, in an embodiment, the hydrogen-inhibiting negative electrode lead paste for the lead-carbon battery comprises the following components in parts by mass: 100-105 parts of lead powder, 0.008-15 parts of activated carbon material, 0.08-0.12 part of binder, 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate, 0.08-0.09 part of hydrogen inhibitor and 10-14 parts of sulfuric acid; wherein the mass of the hydrogen inhibitor is 6-10% of that of the activated carbon material, and the hydrogen inhibitor consists of bismuth oxide and gallium oxide. According to the hydrogen inhibition negative electrode lead plaster for the lead-carbon battery, the hydrogen inhibition agent consisting of bismuth oxide and gallium oxide is added, the mass of the hydrogen inhibition agent is 6% -10% of that of the active carbon material, and compared with the traditional method of adding the hydrogen inhibition agent with a single component, the hydrogen inhibition agent consisting of bismuth oxide and gallium oxide has a synergistic effect in hydrogen inhibition, has a better synergistic hydrogen evolution inhibition effect, and can further improve the capacity of the lead-carbon battery.
It should be further noted that although the addition of carbon can improve the cycle life of the battery, the addition of carbon material, carbon, has a low hydrogen evolution potential relative to lead, which results in a hydrogen evolution reaction easily occurring during the charging process of the lead-carbon battery, especially in the late charging period. The research of the applicant finds that the hydrogen evolution potential is higher by adding the hydrogen inhibitor consisting of bismuth oxide and gallium oxide, and the hydrogen evolution potential can be transferred by about 150-200 millivolts compared with the original carbon material, so that the hydrogen evolution inhibiting effect is relatively good. When bismuth oxide and gallium oxide are added separately, the hydrogen evolution potential can only be shifted by about 100 millivolts to 135 millivolts compared with the original carbon material. Therefore, the bismuth oxide and the gallium oxide are added simultaneously, and have a certain synergistic effect, so that the bismuth oxide and the gallium oxide can have a better synergistic inhibition effect on hydrogen evolution, and further the capacity of the lead-carbon battery can be further improved. In the embodiment, through the hydrogen inhibitor consisting of bismuth oxide and gallium oxide, and the mass of the hydrogen inhibitor is 6-10% of the mass of the activated carbon material, the applicant researches and discovers that when the content of the mixed hydrogen inhibitor is lower than 6% of the mass of the activated carbon material, especially when the activated carbon material is ordered mesoporous carbon, the synergistic effect of bismuth oxide and gallium oxide is limited, and when the mixed hydrogen inhibitor exceeds 10%, the synergistic effect cannot be further improved. And when the mass of the hydrogen agent is 6-10% of the mass of the activated carbon material, the synergistic effect is more suitable. Preferably, in the hydrogen inhibitor, the mass ratio of the bismuth oxide to the gallium oxide is "0.98-1.05": "2.1-2.3". Thus, the applicant has found that the ratio of bismuth oxide to gallium oxide is 0.98-1.05 ": 2.1-2.3, the hydrogen evolution potential can be transferred to about 160-200 millivolts compared with the original carbon material, so that the hydrogen evolution inhibition effect is relatively good, and the synergistic effect is better. More preferably, in the hydrogen inhibitor, the mass ratio of the bismuth oxide to the gallium oxide is "1.01 to 1.03": "2.2-2.27". More preferably, in the hydrogen inhibitor, the mass ratio of the bismuth oxide to the gallium oxide is 1.025: 2.24. thus, the applicant has found that the ratio of bismuth oxide to gallium oxide is 0.98-1.05 ": 2.1-2.3, the hydrogen evolution potential can be transferred to about 172-200 millivolts compared with the original carbon material, so that the hydrogen evolution inhibition effect is relatively good, and the synergistic effect is better.
According to the hydrogen inhibition negative electrode lead plaster for the lead-carbon battery, the hydrogen inhibition agent consisting of bismuth oxide and gallium oxide is added, the mass of the hydrogen inhibition agent is 6% -10% of that of the active carbon material, and compared with the traditional method of adding the hydrogen inhibition agent with a single component, the hydrogen inhibition agent consisting of bismuth oxide and gallium oxide has a synergistic effect in hydrogen inhibition, has a better synergistic hydrogen evolution inhibition effect, and can further improve the capacity of the lead-carbon battery.
In an embodiment, the hydrogen-suppressing negative electrode lead paste for a lead-carbon battery is as defined in any one of claims 1 to 8, and the method for preparing the hydrogen-suppressing negative electrode lead paste for a lead-carbon battery comprises the following steps: uniformly mixing the hydrogen inhibitor and the activated carbon material to obtain a first mixture; uniformly mixing lead powder and the first mixture to obtain a second mixture, and uniformly mixing a binder, sodium lignosulphonate, humic acid, barium sulfate and the second mixture to obtain a third mixture; and adding sulfuric acid into the third mixture, and mechanically stirring and mixing to obtain the hydrogen-inhibiting negative electrode lead paste for the lead-carbon battery. Thus, the negative electrode lead paste can be prepared well.
The application also provides a hydrogen suppression negative plate of the lead-carbon battery, which is prepared by coating the negative lead plaster in any embodiment on a negative grid. Or, the lead-carbon battery negative electrode lead paste is coated on a negative electrode grid.
The application also provides a lead-carbon battery, which comprises the negative plate of the lead-carbon battery as described in any one of the above embodiments. Alternatively, the negative electrode of the lead-carbon battery described in any of the above embodiments is used.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features. It should be noted that "in one embodiment," "for example," "as another example," and the like, are intended to illustrate the application and are not intended to limit the application. The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The lead-carbon battery negative electrode lead paste is characterized by comprising the following components in parts by mass:
100-105 parts of lead powder, 7-15 parts of ordered mesoporous carbon pulp, 0.08-0.12 part of binder, 0.12-0.18 part of sodium lignosulfonate, 0.18-0.24 part of humic acid, 0.17-0.25 part of barium sulfate, 0.08-0.13 part of hydrogen inhibitor and 10-14 parts of sulfuric acid; the ordered mesoporous carbon-carbon slurry comprises hydrogen peroxide, ordered mesoporous carbon and ozone water, wherein the mass ratio of the hydrogen peroxide to the ordered mesoporous carbon to the ozone water is 80-100: 1: 10-12, wherein the mass of the ordered mesoporous carbon powder is 0.008-0.012 of the mass of the lead powder.
2. The lead-carbon battery negative electrode lead paste as defined in claim 1, wherein the binder is short fibers.
3. The lead-carbon battery negative electrode lead paste as defined in claim 1, wherein the binder is water-soluble carboxymethyl cellulose, polyvinyl alcohol, starch or dextrin.
4. The lead-carbon battery negative electrode lead paste as defined in claim 1, wherein the sulfuric acid has a density of 1.325 g/ml.
5. The lead-carbon battery negative electrode lead paste as defined in claim 1, wherein the hydrogen inhibitor is indium oxide.
6. The lead-carbon battery negative electrode lead paste as defined in claim 1, wherein the hydrogen peroxide solution is a hydrogen peroxide solution with a mass fraction of 10%.
7. The lead-carbon battery negative electrode lead paste as claimed in claim 1, wherein the preparation method of the ordered mesoporous carbon-carbon slurry comprises the following steps:
mixing ozone water, hydrogen peroxide and ordered mesoporous carbon, and reacting for 2-2.5 hours at 60-68 ℃ to prepare the ordered mesoporous carbon slurry.
8. The lead-carbon battery negative electrode lead paste as defined in claim 7, wherein the concentration of ozone in the ozone water is 7mg/L-12 mg/L.
9. A method for preparing the lead-carbon battery negative electrode lead paste, which is characterized in that the lead-carbon battery negative electrode lead paste is the lead-carbon battery negative electrode lead paste as defined in any one of claims 1 to 8, and the method for preparing the lead-carbon battery negative electrode lead paste comprises the following steps:
mixing and stirring lead powder, the ordered mesoporous carbon slurry, the binder, sodium lignosulfonate, humic acid, barium sulfate and a hydrogen inhibitor, adding sulfuric acid, and mechanically stirring and mixing to obtain the lead-carbon battery cathode lead paste.
10. The preparation method of claim 9, wherein the lead powder, the ordered mesoporous carbon slurry, the binder, the sodium lignosulfonate, the humic acid, the barium sulfate and the hydrogen inhibitor are mixed and stirred, and the lead powder and the ordered mesoporous carbon slurry are firstly mixed and dispersed uniformly, and then the binder, the sodium lignosulfonate, the humic acid, the barium sulfate and the hydrogen inhibitor are added.
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| CN103000882A (en) * | 2012-12-28 | 2013-03-27 | 湖南丰日电源电气股份有限公司 | Lead carbon battery cathode lead plaster and preparation method thereof |
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Denomination of invention: Lead paste for negative electrode of lead carbon battery and its preparation method Effective date of registration: 20230317 Granted publication date: 20210420 Pledgee: Bank of Beijing Limited by Share Ltd. Shenzhen branch Pledgor: ZHAOQING LEOCH BATTERY TECHNOLOGY Co.,Ltd. Registration number: Y2023980035318 |
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