A high-power lead-acid battery electrolyte and a preparation method thereof

Abstract

The application discloses a high-power lead-acid battery electrolyte and a preparation method thereof, and belongs to the technical field of electrochemistry. The lead-acid battery electrolyte raw materials comprise 40-60 parts of sulfuric acid, 40-60 parts of deionized water, 5-10 parts of phosphoric acid, 0.5-2 parts of fumed silica, 0.5-1 part of lithium carbonate, 0.2-1 part of anhydrous sodium sulfate, 0.2-0.5 part of lithium iodide, 0.1-0.5 part of stannous sulfate, 0.1-0.3 part of isopropyl alcohol, 0.1-0.2 part of acrylamide, 0.02-0.1 part of an additive, and 0.005-0.01 part of a defoaming agent. The additive containing a hindered phenol structure, a benzimidazole structure and a hydroxyl group has good compatibility with the remaining raw materials, can be uniformly dispersed and stably exist in the electrolyte, and can further produce the effects of stable and effective antioxidation, anticorrosion and deposit removal. Therefore, the additive added into the electrolyte can improve the charge-discharge performance of the storage battery and prolong the service life of the storage battery.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of electrochemistry, and particularly relates to a high-power lead-acid battery electrolyte and a preparation method thereof. BACKGROUND

[0002] The lead-acid battery occupies a pivotal position in the field of secondary batteries due to its excellent performance-price ratio. Among all aqueous solution power systems, the lead-acid battery has a high working voltage, good large-current discharge performance and high-low temperature discharge performance, and is suitable for both floating use and starting and cycling use. The gel battery represents the advanced level of the development of the lead-acid battery, and the gel electrolyte is a key technology for manufacturing the gel battery.

[0003] The main role of the existing additive of the lead-acid battery is to prevent the lead plate of the battery from generating deposits and remove the lead sulfate deposits on the corroded lead plate. However, the prepared additive is convenient to use and can maintain the original performance of the battery, but the compatibility between the additive and the remaining raw materials is poor, so the additive cannot play a long-term role. SUMMARY

[0004] The present application aims to overcome the defects of the prior art and provides a high-power lead-acid battery electrolyte and a preparation method thereof.

[0005] The object of the present application can be achieved by the following technical solutions.

[0006] A high-power lead-acid battery electrolyte comprises the following raw materials by weight: sulfuric acid 40-60 parts, deionized water 40-60 parts, phosphoric acid 5-10 parts, fumed silica 0.5-2 parts, lithium carbonate 0.5-1 part, anhydrous sodium sulfate 0.2-1 part, lithium iodide 0.2-0.5 part, stannous sulfate 0.1-0.5 part, isopropyl alcohol 0.1-0.3 part, acrylamide 0.1-0.2 part, an additive 0.02-0.1 part, and an antifoaming agent 0.005-0.01 part.

[0007] Further, the additive is prepared by the following steps:

[0008] S1, under nitrogen protection, 3-amino-1,2-propanediol, triethylamine and ethanol are fully stirred to be uniformly mixed, then heated to 60 DEG C, and then 4-chloro-1-butene is slowly added, after the addition is completed, the reaction is kept at 60 DEG C for 3 hours, then cooled to room temperature, and then distilled under reduced pressure to obtain an intermediate 1; the amount ratio of 3-amino-1,2-propanediol, 4-chloro-1-butene, triethylamine and ethanol is 9.9g:10.1mL:18.1mL:120mL;

[0009] Triethylamine as an acid-binding agent, control 3-amino-1,2-propanediol and 4-chloro-1-butene molar ratio of 1.05-1.1:1, then 3-amino-1,2-propanediol -NH2 and 4-chloro-1-butene -Cl under heating nucleophilic substitution reaction, the reaction process is as follows:

[0010]

[0011] S2, room temperature, intermediate 1, pyridine and dimethyl sulfoxide were stirred to mix evenly, heated to 80℃, then slowly add 2,6-di-tert-butyl-4-bromomethyl phenol, after the addition of 80℃ for 5h, the reaction was completed after cooling to room temperature, reduced pressure distillation, to obtain intermediate 2; the amount of intermediate 1, 2,6-di-tert-butyl-4-bromomethyl phenol, pyridine and dimethyl sulfoxide is 14.8g:28.4g:9.2mL:200mL;

[0012] Pyridine as an acid-binding agent, control intermediate 1 and 2,6-di-tert-butyl-4-bromomethyl phenol molar ratio of 1.05-1.1:1, then 2,6-di-tert-butyl-4-bromomethyl phenol -Br and intermediate 1 -NH- under heating nucleophilic substitution reaction, the reaction process is as follows:

[0013]

[0014] S3, room temperature, intermediate 2, 2-mercapto benzimidazole, benzoin dimethyl ether and dimethyl sulfoxide were stirred to mix evenly, then placed under 365nm ultraviolet light for 15min, the reaction was completed after reduced pressure distillation, to obtain the additive; the amount of intermediate 2, 2-mercapto benzimidazole, benzoin dimethyl ether and dimethyl sulfoxide is 30.9g:8.9g:0.44g:200mL.

[0015] Benzoin dimethyl ether as a photoinitiator, control intermediate 2 and 2-mercapto benzimidazole molar ratio of 1:1, then the carbon-carbon double bond of intermediate 2 and 2-mercapto benzimidazole -SH occur mercapto-alkene click reaction, the reaction process is as follows:

[0016]

[0017] The additive contains hindered phenol structure and benzimidazole structure, which can synergistically play the roles of antioxidation, anticorrosion and deposit removal. In the process of redox reaction of the storage battery, the additive can prevent the formation and deposition of lead sulfate. Meanwhile, the additive contains multiple hydroxyl groups, which can form hydrogen bond interaction with the hydroxyl groups in phosphoric acid, fumed silica and deionized water. Therefore, the additive has good compatibility with the other raw materials, can be uniformly dispersed and stably exist in the electrolyte, and further plays the stable and effective roles of antioxidation, anticorrosion and deposit removal. Therefore, the additive can improve the charge-discharge performance of the storage battery and prolong the service life of the storage battery.

[0018] Further, the defoaming agent is one or both of glycerol polyoxypropylene polyoxyethylene ether and tributyl phosphate.

[0019] A preparation method of a high-power lead-acid battery electrolyte, comprising the following steps:

[0020] The raw materials are weighed by weight parts, and then the phosphoric acid, anhydrous sodium sulfate, stannous sulfate, lithium iodide, lithium carbonate and sulfuric acid are fully stirred and mixed to obtain a premix solution for standby; then the deionized water and fumed silica are mixed in a glue making machine, and the isopropyl alcohol and acrylamide are added under stirring, and then mixed uniformly, and then mixed with the premix solution, and then continuously stirred and added with the defoaming agent and the additive, and then stirred uniformly to obtain the high-power lead-acid battery electrolyte.

[0021] The additive contains hindered phenol structure, benzimidazole structure and multiple hydroxyl groups, and therefore has good compatibility with the other raw materials, can be uniformly dispersed and stably exist in the electrolyte, and further plays the stable and effective roles of antioxidation, anticorrosion and deposit removal. Therefore, the additive can improve the charge-discharge performance of the storage battery and prolong the service life of the storage battery. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0023] Embodiment 1

[0024] The additive is prepared, and the specific steps are as follows:

[0025] S1. Under nitrogen protection, 9.9 g of 3-amino-1,2-propylene glycol, 18.1 mL of triethylamine, and 120 mL of ethanol were thoroughly stirred until uniformly mixed. After heating to 60°C, 10.1 mL of 4-chloro-1-butene was slowly added. After the addition was complete, the mixture was kept at 60°C for 3 h. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure to obtain intermediate 1.

[0026] S2. 14.8 g of intermediate 1, 9.2 mL of pyridine, and 200 mL of dimethyl sulfoxide were stirred thoroughly at room temperature until uniformly mixed. The mixture was heated to 80° C., and then 28.4 g of 2,6-di-tert-butyl-4-bromomethylphenol was slowly added. After the addition was complete, the mixture was kept at 80° C. for 5 h. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure to obtain intermediate 2.

[0027] S3. At room temperature, 30.9 g of intermediate 2, 8.9 g of 2-mercaptobenzimidazole, 0.44 g of benzoin dimethyl ether and 200 mL of dimethyl sulfoxide were stirred thoroughly until uniformly mixed, and then irradiated under a 365 nm ultraviolet lamp for 15 min. After the reaction was completed, the mixture was distilled under reduced pressure to obtain an auxiliary agent.

[0028] Example 2

[0029] Prepare lead-acid battery electrolyte, the specific steps are as follows:

[0030] Weigh each raw material by weight, then thoroughly stir 5 parts of phosphoric acid, 0.2 parts of anhydrous sodium sulfate, 0.1 parts of stannous sulfate, 0.2 parts of lithium iodide, 0.5 parts of lithium carbonate and 40 parts of sulfuric acid until mixed uniformly to obtain a premixed solution for later use; then, mix 40 parts of deionized water and 0.5 parts of fumed silica in a gel making machine, add 0.1 parts of isopropyl alcohol and 0.1 parts of acrylamide while stirring, mix uniformly, and then mix with the premixed solution, continue stirring, add 0.005 parts of glycerol polyoxypropylene polyoxyethylene ether and 0.02 parts of the auxiliary agent prepared in Example 1, and stir uniformly to obtain a lead-acid battery electrolyte.

[0031] Example 3

[0032] Prepare lead-acid battery electrolyte, the specific steps are as follows:

[0033] The raw materials were weighed in parts by weight, and 8 parts of phosphoric acid, 0.7 parts of anhydrous sodium sulfate, 0.4 parts of stannous sulfate, 0.3 parts of lithium iodide, 0.8 parts of lithium carbonate and 56 parts of sulfuric acid were thoroughly stirred until uniformly mixed to obtain a premixed solution for later use; 55 parts of deionized water and 1.2 parts of fumed silica were then mixed in a gel making machine, 0.2 parts of isopropyl alcohol and 0.15 parts of acrylamide were added while stirring, and the mixture was uniformly mixed and then mixed with the premixed solution. Stirring was continued and 0.008 parts of tributyl phosphate and 0.07 parts of the auxiliary agent prepared in Example 1 were added. After stirring, a lead-acid battery electrolyte was prepared.

[0034] Example 4

[0035] The lead-acid battery electrolyte was prepared according to the following steps:

[0036] The raw materials were weighed by parts by weight, and then 10 parts of phosphoric acid, 1 part of anhydrous sodium sulfate, 0.5 parts of stannous sulfate, 0.5 parts of lithium iodide, 1 part of lithium carbonate and 60 parts of sulfuric acid were fully stirred to be mixed uniformly to obtain a premix solution for standby; then 60 parts of deionized water and 2 parts of fumed silica were mixed in a glue making machine, 0.3 parts of isopropyl alcohol and 0.2 parts of acrylamide were added under stirring, and after mixing uniformly, the premix solution was mixed, and then 0.01 parts of glycerol polyoxypropylene polyoxyethylene ether and 0.1 parts of the additive prepared in Example 1 were added and stirred uniformly to obtain the lead-acid battery electrolyte.

[0037] Comparative Example 1

[0038] The lead-acid battery electrolyte was prepared according to the following steps:

[0039] The remaining steps were unchanged, only the additive of Example 2 was replaced by 0.09 parts of antioxidant 264 and 0.01 parts of p-chlorobenzyl benzimidazole to prepare the lead-acid battery electrolyte.

[0040] Performance test

[0041] The lead-acid battery electrolytes prepared in Examples 2-4 and Comparative Example 1 were used in lead-acid batteries, and the performance comparison with other lead-acid batteries using ordinary electrolyte was tested as shown in the following table:

[0042]

[0043] In the description of the specification, the description of the reference terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are contained in at least one embodiment or example of the present application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0044] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the scope of the invention or exceed the scope defined by the present claims, which shall be within the protection scope of the present application.

Claims

1. A high-power lead-acid battery electrolyte, characterized in that: The invention comprises the following raw materials in parts by weight: 40-60 parts of sulfuric acid, 40-60 parts of deionized water, 5-10 parts of phosphoric acid, 0.5-2 parts of fumed silica, 0.5-1 parts of lithium carbonate, 0.2-1 parts of anhydrous sodium sulfate, 0.2-0.5 parts of lithium iodide, 0.1-0.5 parts of stannous sulfate, 0.1-0.3 parts of isopropyl alcohol, 0.1-0.2 parts of acrylamide, 0.02-0.1 parts of an auxiliary agent, and 0.005-0.01 parts of a defoaming agent; Wherein, the auxiliary agent is prepared by the following steps: S1. Under nitrogen protection, 3-amino-1,2-propanediol, triethylamine, and ethanol were stirred, heated to 60°C, and 4-chloro-1-butene was added. The mixture was reacted for 3 h, cooled, and distilled under reduced pressure to obtain intermediate 1. S2. Stir intermediate 1, pyridine and dimethyl sulfoxide, heat to 80°C, add 2,6-di-tert-butyl-4-bromomethylphenol, react for 5 hours, cool, and distill under reduced pressure to obtain intermediate 2; S3. At room temperature, the intermediate 2, 2-mercaptobenzimidazole, benzoin dimethyl ether and dimethyl sulfoxide were stirred, irradiated under a 365nm ultraviolet lamp for 15 minutes, and distilled under reduced pressure to obtain an auxiliary agent. 。 2. A high-power lead-acid battery electrolyte according to claim 1, characterized in that: The usage ratio of 3-amino-1,2-propanediol, 4-chloro-1-butene, triethylamine and ethanol in step S1 is 9.9 g:10.1 mL:18.1 mL:120 mL.

3. The high-power lead-acid battery electrolyte according to claim 1, characterized in that: The usage ratio of the intermediate 1 in step S2, 2,6-di-tert-butyl-4-bromomethylphenol, pyridine and dimethyl sulfoxide is 14.8 g:28.4 g:9.2 mL:200 mL.

4. The high-power lead-acid battery electrolyte according to claim 1, characterized in that: The usage ratio of intermediate 2, 2-mercaptobenzimidazole, benzoin dimethyl ether and dimethyl sulfoxide in step S3 is 30.9 g:8.9 g:0.44 g:200 mL.

5. The high-power lead-acid battery electrolyte according to claim 1, characterized in that: The defoaming agent is one or both of glycerol polyoxypropylene polyoxyethylene ether and tributyl phosphate.

6. The high-power lead-acid battery electrolyte according to claim 1, characterized in that: The preparation method of the high-power lead-acid battery electrolyte comprises the following steps: The raw materials are weighed in parts by weight, and phosphoric acid, anhydrous sodium sulfate, stannous sulfate, lithium iodide, lithium carbonate and sulfuric acid are thoroughly stirred until they are evenly mixed to obtain a premixed solution for later use. Subsequently, deionized water and fumed silica are mixed in a gel making machine, and isopropyl alcohol and acrylamide are added while stirring. After mixing evenly, the mixture is mixed with the premixed solution, and the stirring is continued. A defoaming agent and an auxiliary agent are added, and after stirring evenly, a high-power lead-acid battery electrolyte is prepared.

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