Preparation method of aluminum lignosulfonate and application thereof in preparation of lead-acid storage battery

Abstract

The present application relates to a kind of preparation method of aluminum lignosulfonate and application in lead-acid battery preparation.The present application first uses "ion exchange method", with lead-acid battery sodium lignosulfonate as raw material to prepare aluminum lignosulfonate.The above preparation method is simple, reaction condition is easy to control, is conducive to environmental protection, easy to realize scale production, with good economic benefit and social benefit.In addition, the present application also provides the application of aluminum lignosulfonate as lead-acid battery additive, which is applied to battery cathode coating, can effectively improve the anti-freezing performance of battery, improve battery capacity.

Description

Technical Field

[0001] This invention belongs to the field of lignin synthesis technology, specifically relating to a method for preparing aluminum lignin sulfonate based on the ion exchange approach and the application of aluminum lignin sulfonate as an additive in the preparation of lead-acid batteries. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Lignin, also known as lignin, is usually isolated from trees. It is a major component of the second cell wall of plants and is a complex phenolic natural polymer formed by p-coumarol, coniferol, 5-hydroxyconiferol, and sinigrin. Sulfonation of lignin to obtain lignin sulfonates is the foundation and prerequisite for the application of lignin.

[0004] Lignin sulfonate, also known as sulfonated lignin, can be obtained by sulfonation of lignin and is a byproduct of sulfite pulping. It has strong dispersibility, varying to different degrees depending on its molecular weight and functional groups. It is a surface-active substance that can adsorb onto the surface of various solid particles and can perform metal ion exchange. Due to the presence of various active groups in its structure, it can undergo condensation or hydrogen bonding with other compounds. It has a wide range of applications, such as being used as a dye dispersant, pesticide production adjuvant, concrete water-reducing agent, ceramic reinforcing agent, protein precipitant, carbon black granulation binder, asphalt emulsifier, oil extraction adjuvant, rubber reinforcing agent, conductive polymer dopant, and battery plate expansion agent.

[0005] Currently, the main expanding agent used in battery plates is sodium lignosulfonate, which is mixed into the active material of the negative electrode during paste preparation. During discharge, a rough, thick, porous PbSO4 layer is formed on the lead negative electrode, thereby improving low-temperature and high-rate discharge capabilities; during charging, the organic expanding agent plays a role in preventing shrinkage. Because the expanding agent is adsorbed onto the lead, it contributes to the expansion of the Pb-containing electrode. 2+ When electrodeposited as lead, the agglomeration between particles is prevented, thus maintaining a sponge-like lead with a well-developed surface and porous structure, thereby improving the battery's lifespan.

[0006] Charge acceptability is one of the important performance indicators for lead-acid batteries. It generally refers to the charging current value (expressed in ampere-hours) that a battery can accept within a certain time under specified temperature, voltage, and state of charge. Typically, the addition of sodium lignosulfonate can affect the charge acceptability of lead-acid batteries, leading to a decrease in their charge acceptability. Summary of the Invention

[0007] This invention uses sodium lignosulfonate as a raw material to prepare aluminum lignosulfonate by "ion replacement method" and provides the application of aluminum lignosulfonate as a negative electrode additive for lead-acid batteries. This application method can not only maintain the capacity and low-temperature performance of lead-acid batteries, but also effectively improve the charge acceptance of lead-acid batteries, thus significantly improving the performance of lead-acid batteries.

[0008] Based on the above-mentioned technical effects, the present invention provides the following technical solution:

[0009] In a first aspect, the present invention provides a method for preparing aluminum lignosulfonate, comprising the following steps: adding calcium hydroxide solution to sodium lignosulfonate mother liquor and stirring for a period of time to separate calcium lignosulfonate from the reaction system; preparing the calcium lignosulfonate into a slurry and adding aluminum salt; heating to carry out the reaction; filtering after the reaction is completed; and drying the filtrate to obtain aluminum lignosulfonate.

[0010] In the above preparation method, the sodium lignosulfonate mother liquor is prepared by adding sodium lignosulfonate for lead-acid batteries to water and stirring until the sodium lignosulfonate is completely dissolved. The preferred concentration range of the mother liquor is 0-10% and not 0. The sodium content in the sodium lignosulfonate of the raw material is preferably 3-7%, more preferably 4-6%, and specific examples are 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, and 5.3%.

[0011] Preferably, in the preparation process of the calcium lignosulfonate, the sodium lignosulfonate and calcium hydroxide are added in a ratio of sodium to calcium of 1:0.86 to 1:0.89 by weight.

[0012] Furthermore, after adding calcium hydroxide solution to the sodium lignosulfonate mother liquor, the reaction is carried out at room temperature. During the reaction, the mixture is continuously stirred until no more calcium lignosulfonate precipitate is formed. The reaction time is more than 0.5 hours, preferably 0.5 hours to 2 hours.

[0013] Furthermore, the above-mentioned calcium hydroxide solution is a clear solution of calcium hydroxide, prepared as follows: add calcium oxide to water and filter to obtain the supernatant.

[0014] Furthermore, the separation of calcium lignosulfonate also includes a washing step, in which water is added to wash the separated calcium lignosulfonate to remove unreacted sodium lignosulfonate from the mother liquor.

[0015] Preferably, in the process of preparing aluminum lignosulfonate from calcium lignosulfonate, the calcium lignosulfonate obtained above is mixed with water to form a slurry, and the concentration of the slurry is 0-10% and not 0.

[0016] Furthermore, the aluminum salt is added to the above slurry in a weight ratio of lignosulfonate calcium to calcium and aluminum salt of 1:0.45 to 1:0.47.

[0017] Furthermore, the aluminum salt is a salt composed of aluminum ions and acid radical anions, such as aluminum trichloride, aluminum sulfate, alum, or their hydrates; in a more preferred embodiment of the present invention, the aluminum salt is aluminum sulfate or aluminum sulfate hydrate.

[0018] Furthermore, the heating temperature is 90°C or higher, stirring is required during the reaction, and the heating reaction time is 1.5 to 3 hours.

[0019] Furthermore, after the heating reaction is completed, the reaction system is filtered, and the filtrate is the aluminum lignosulfonate mother liquor. The filtrate is dried to obtain aluminum lignosulfonate, and the drying method is oven drying or spray drying.

[0020] In a second aspect, the present invention provides aluminum lignosulfonate obtained by the preparation method described in the first aspect.

[0021] In a third aspect, the present invention provides the application of the aluminum lignosulfonate described in the second aspect in the following fields:

[0022] (1) Applications in the chemical industry;

[0023] (2) Applications in the construction field;

[0024] (3) Applications in the field of electrochemistry.

[0025] As a natural renewable resource, lignin derivatives can effectively compensate for the increasingly depleted fossil resources, and their application fields are also very wide. This invention provides an aluminum lignin sulfonate, which has the characteristics of good dispersibility, stable chemical properties, good grinding aid, and excellent weather resistance compared with other commonly used lignin sulfonates. Based on the above physicochemical properties, those skilled in the art can expect that it can maintain the good solubility, dispersibility and stability of existing lignin sulfonates.

[0026] In the preferred embodiment, the chemical field described in aspect (1) above includes, but is not limited to, applications in the processing and modification of polymer materials, dispersion and bonding of chemical products, preparation of oilfield chemicals or bio-fermentation substrates. Specific examples include dye dispersants, pesticide production auxiliaries, carbon black granulation binders, carbon nanotube dispersants, asphalt emulsifiers, oil extraction auxiliaries, rubber reinforcing agents, flame retardant materials, catalysts and their carriers, protein precipitants, microbial culture media, organic fertilizers, etc.

[0027] In the above (2) applications, the aluminum lignosulfonate can be used to prepare a building material additive, such as a concrete water-reducing agent or a ceramic reinforcing agent;

[0028] In the above-mentioned application (3), the aluminum lignosulfonate can be used to prepare conductive polymer dopants or electrolytes, etc.

[0029] Regarding the application of the aforementioned aluminum lignosulfonate, this invention has verified its application in the field of electrochemistry, specifically providing the application of the aforementioned aluminum lignosulfonate as an additive for lead-acid batteries. According to the verification results, as an additive, it can not only effectively replace the existing sodium lignosulfonate, but also effectively improve the antifreeze performance of the battery.

[0030] In a fourth aspect, the present invention provides the application of the aluminum lignosulfonate described in the second aspect in the preparation of lead-acid batteries.

[0031] The main application method described in the fourth aspect above is to use the aluminum lignosulfonate as an additive for lead-acid batteries.

[0032] In a fifth aspect, the present invention provides a cathode for a lead-acid battery, the cathode comprising a grid and a coating, wherein the coating comprises aluminum lignosulfonate as described in the second aspect.

[0033] Preferably, in the above-mentioned cathode coating of the storage battery, the amount of aluminum lignosulfonate added is 0‰ to 10‰ and not 0; in one embodiment of the present invention, lead paste is used as the matrix, and the proportions of barium sulfate, carbon black and aluminum lignosulfonate in the cathode coating are 8-12‰, 2-5‰ and 1-3‰, respectively; further, the proportions of barium sulfate, carbon black and aluminum lignosulfonate in the lead paste are 9-11%, 2-4% and 2%, respectively.

[0034] In a sixth aspect, the present invention provides a lead-acid battery, wherein the lead-acid battery includes the cathode described in the first aspect.

[0035] The beneficial effects of one or more of the above technical solutions are:

[0036] 1. The method for preparing aluminum lignosulfonate provided by the present invention has the technical advantages of simple operation, mild reaction conditions and high yield. The intermediate process of the preparation method - calcium lignosulfonate - after centrifugation, the remaining filtrate contains unreacted sodium lignosulfonate and sodium hydroxide, which can be reused to prepare sodium lignosulfonate mother liquor.

[0037] 2. Existing lead-acid batteries typically use sodium lignosulfonate as an additive to improve the low-temperature discharge performance of the battery. This invention has demonstrated that aluminum lignosulfonate can effectively improve the battery's capacitance and charging performance under low-temperature conditions compared to sodium lignosulfonate, overcoming the shortcomings of sodium lignosulfonate and can be used as a superior lead-acid battery additive. Attached Figure Description

[0038] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0039] Figure 1 This is a flowchart illustrating the preparation of aluminum lignosulfonate as described in this invention;

[0040] Figure 2 Electron micrograph of aluminum lignosulfonate prepared in Example 1;

[0041] Figure 3 The analysis was performed using EDS energy dispersive spectroscopy of aluminum lignosulfonate as described in Example 1. Detailed Implementation

[0042] It should be noted that the following detailed description is illustrative and intended to provide further explanation of the invention. Unless otherwise specified, 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 pertains.

[0043] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0044] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0045] Example 1

[0046] Using sodium lignosulfonate, commonly used in lead-acid batteries, as raw material with a sodium content of 5%, 10g of sodium lignosulfonate was dissolved in 200g of pure water to prepare a sodium lignosulfonate mother liquor in a beaker. 0.814g of slaked lime was added to the prepared sodium lignosulfonate mother liquor, and after stirring for 1 hour, the resulting calcium lignosulfonate was separated by centrifugation. The separated calcium lignosulfonate was transferred to a beaker, 200g of pure water was added, and the mixture was stirred to form a calcium lignosulfonate slurry. 6.97g of aluminum sulfate octadechydrate was added to the calcium lignosulfonate slurry, and the mixture was heated to above 90℃ and stirred for 2 hours. After cooling, the calcium sulfate residue was separated by filtration. The filtrate was spray-dried to obtain aluminum lignosulfonate (e.g., ...). Figure 2 and 3 (As shown).

[0047] Example 2

[0048] Using sodium lignosulfonate, commonly used in lead-acid batteries, as raw material with a sodium content of 4%, 8g of sodium lignosulfonate was dissolved in 200g of pure water to prepare a sodium lignosulfonate mother liquor in a beaker. 0.814g of quicklime was added to the prepared sodium lignosulfonate mother liquor, and after stirring for 0.8 hours, the resulting calcium lignosulfonate was separated by centrifugation. The separated calcium lignosulfonate was transferred to a beaker, 200g of pure water was added, and the mixture was stirred to form a calcium lignosulfonate slurry. 6.97g of aluminum sulfate octadechydrate was added to the calcium lignosulfonate slurry, and the mixture was heated to above 95℃ and stirred for 1.5 hours. After cooling, the calcium sulfate residue was separated by filtration, and the filtrate was spray-dried to obtain aluminum lignosulfonate.

[0049] Example 3

[0050] Using sodium lignosulfonate, commonly used in lead-acid batteries, as raw material with a sodium content of 6%, 12g of sodium lignosulfonate was dissolved in 200g of pure water to prepare a sodium lignosulfonate mother liquor in a beaker. 0.814g of quicklime was added to the prepared sodium lignosulfonate mother liquor, and after stirring for 1.5 hours, the resulting calcium lignosulfonate was separated by centrifugation. The separated calcium lignosulfonate was transferred to a beaker, 200g of pure water was added, and the mixture was stirred to form a calcium lignosulfonate slurry. 6.97g of aluminum sulfate octadechydrate was added to the calcium lignosulfonate slurry, and the mixture was heated to above 90℃ and stirred for 1.8 hours. After cooling, the calcium sulfate residue was separated by filtration. The filtrate was dried and pulverized to obtain aluminum lignosulfonate.

[0051] Example 4

[0052] The aluminum lignosulfonate prepared in Example 1 (at an addition rate of 2‰), barium sulfate (at an addition rate of 10‰), and carbon black (at an addition rate of 3‰) were mixed evenly in lead paste, coated onto a cathode grid, cured, and assembled into a 5Ah single-cell test cell with a 3-positive-2-negative structure. After acidification, the performance indicators of the single-cell test cell were tested. A comparison was made using the same amount of sodium lignosulfonate as a raw material; the results are shown in Table 1.

[0053] Table 1 Performance Test of 5Ah Single Cell Battery

[0054]

[0055] Example 5

[0056] The aluminum lignosulfonate from Example 1 was mixed evenly with barium sulfate and carbon black in lead paste, then coated onto the cathode grid plate. After curing, a 20Ah single-cell test cell with a 5-positive and 4-negative structure was assembled. After acidification, the performance indicators of the single-cell test cell were tested. The results of the comparison cell using the same amount of sodium lignosulfonate are shown in Table 2.

[0057] Table 2 Performance Tests of 20Ah Single Cell Test Batteries

[0058]

[0059]

[0060] Example 6

[0061] The aluminum lignosulfonate from Example 1 was mixed evenly with barium sulfate and carbon black in lead paste, then coated onto the cathode grid plate. After curing, a 60Ah single-cell test cell with an 8-positive and 7-negative structure was assembled. After acidification, the performance indicators of the single-cell test cell were tested. The results of the comparison cell using the same amount of sodium lignosulfonate are shown in Table 3.

[0062] Table 3 Performance Tests of 60Ah Single Cell Test Batteries

[0063]

[0064] As can be seen from the data in Tables 4-6 of the above Examples, compared with sodium lignosulfonate, aluminum lignosulfonate as an additive can effectively improve the low-temperature capacity of lead-acid batteries, increase the charging current and single-cell voltage at low temperatures, which fully demonstrates that aluminum lignosulfonate can improve the performance of lead-acid batteries at low temperatures.

[0065] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An application of aluminum lignosulfonate in the preparation of lead-acid batteries, characterized in that, The preparation method of aluminum lignosulfonate includes the following steps: adding calcium hydroxide solution to sodium lignosulfonate mother liquor and stirring for a period of time, then separating calcium lignosulfonate from the reaction system, preparing the calcium lignosulfonate into a slurry and adding aluminum salt, heating for reaction, filtering after the reaction is completed, retaining part of the filtrate and drying to obtain aluminum lignosulfonate.

2. The application of aluminum lignosulfonate as described in claim 1 in the preparation of lead-acid batteries, characterized in that, The sodium lignosulfonate mother liquor is prepared by adding sodium lignosulfonate for lead-acid batteries to water and stirring until the sodium lignosulfonate is completely dissolved.

3. The application of aluminum lignosulfonate as described in claim 2 in the preparation of lead-acid batteries, characterized in that, The concentration of the mother liquor is in the range of 0 to 10% and is not 0; the sodium content in the sodium lignosulfonate is 3 to 7%.

4. The application of aluminum lignosulfonate as described in claim 1 in the preparation of lead-acid batteries, characterized in that, The sodium lignosulfonate and calcium hydroxide are added in a ratio of sodium to calcium of 1:0.86 to 1:0.89 by weight.

5. The application of aluminum lignosulfonate as described in claim 4 in the preparation of lead-acid batteries, characterized in that, After adding calcium hydroxide solution to the sodium lignosulfonate mother liquor, the reaction is carried out at room temperature. During the reaction, the mixture is stirred continuously until no more calcium lignosulfonate precipitate is formed. The reaction time is more than 0.5 hours. Alternatively, the calcium hydroxide solution can be prepared as follows: add calcium oxide to water and filter to obtain the supernatant. Alternatively, the separation of calcium lignosulfonate may include a washing step, in which water is added to wash the separated calcium lignosulfonate to remove unreacted sodium lignosulfonate from the mother liquor.

6. The application of aluminum lignosulfonate as described in claim 1 in the preparation of lead-acid batteries, characterized in that, In the process of preparing aluminum lignosulfonate from calcium lignosulfonate, the separated calcium lignosulfonate is mixed with water to form a slurry, the concentration of which is 0~10% and not 0; The aluminum salt is added to the above slurry in a weight ratio of lignosulfonate calcium to calcium and aluminum salt of 1:0.45 to 1:0.

47. Alternatively, the aluminum salt is aluminum sulfate or aluminum sulfate hydrate; Alternatively, the heating temperature is 90°C or higher, stirring is required during the reaction, and the heating reaction time is 1.5 to 3 hours; Alternatively, after the heating reaction is complete, the reaction system is filtered, and the filtrate is the aluminum lignosulfonate mother liquor. The filtrate is dried to obtain aluminum lignosulfonate, and the drying method is baking or spray drying.

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