High-power lead-acid battery electrolyte and preparation method thereof

Abstract

The invention 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 comprises the following raw materials: 40 to 60 parts of sulfuric acid, 40 to 60 parts of deionized water, 5 to 10 parts of phosphoric acid, 0.5 to 2 parts of fumed silica, 0.5 to 1 part of lithium carbonate, 0.2 to 1 part of anhydrous sodium sulfate, 0.2 to 0.5 part of lithium iodide, 0.1 to 0.5 part of stannous mono-sulphate, 0.1 to 0.3 part of isopropanol, 0.1 to 0.2 part of acrylamide, 0.02 to 0.1 part of an auxiliary agent and 0.005 to 0.01 part of a defoaming agent. The additive containing the hindered phenol structure, the benzimidazole structure and the hydroxyl group has good compatibility with other raw materials, and can be uniformly dispersed and stably exist in the electrolyte, so that stable and effective effects of oxidation resistance, corrosion resistance and sediment removal are achieved. Therefore, by adding the additive into the electrolyte, the charge-discharge performance of the storage battery can be improved, and the service life of the storage battery can be prolonged.

Description

Technical Field

[0001] The present invention belongs to the field of electrochemical technology, and in particular, relates to a high-power lead-acid battery electrolyte and a preparation method thereof. Background Art

[0002] Lead-acid batteries have a pivotal position in the field of secondary batteries due to their excellent performance-price ratio. Among all aqueous power systems, lead-acid batteries have higher operating voltage, better high-current discharge performance and high and low temperature discharge performance. They are suitable for both floating charge and starting and recycling. Gel batteries represent the advanced level of lead-acid battery development, and colloidal electrolyte is the key technology for making colloidal batteries.

[0003] The main function of existing lead-acid battery additives is to prevent the formation of deposits on the battery lead plate and remove lead sulfate deposits on the corroded lead plate. However, although the currently prepared additives are easy to use and can maintain the original performance of the battery, the additives have poor compatibility with other raw materials and therefore cannot function for a long time. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a high-power lead-acid battery electrolyte and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A high-power lead-acid battery electrolyte 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 isopropanol, 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.

[0007] Furthermore, the auxiliary agent is prepared by the following steps:

[0008] S1. Under nitrogen protection, 3-amino-1,2-propanediol, triethylamine and ethanol were fully stirred until they were uniformly mixed, and then the temperature was raised to 60°C and 4-chloro-1-butene was slowly added. After the addition was completed, the mixture was kept at 60°C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure to obtain intermediate 1; the dosage ratio of 3-amino-1,2-propanediol, 4-chloro-1-butene, triethylamine and ethanol was 9.9 g: 10.1 mL: 18.1 mL: 120 mL;

[0009] Triethylamine is used as an acid binding agent to control the molar ratio of 3-amino-1,2-propylene glycol and 4-chloro-1-butene to be 1.05-1.1:1. Then, the -NH2 of 3-amino-1,2-propylene glycol and the -Cl of 4-chloro-1-butene undergo a nucleophilic substitution reaction under heating. The reaction process is as follows:

[0010]

[0011] S2. At room temperature, the intermediate 1, pyridine and dimethyl sulfoxide were fully stirred until they were uniformly mixed, and then the temperature was raised to 80°C and then 2,6-di-tert-butyl-4-bromomethylphenol was slowly added. After the addition was completed, the mixture was kept at 80°C for 5 hours. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure to obtain the intermediate 2. The usage ratio of the intermediate 1, 2,6-di-tert-butyl-4-bromomethylphenol, pyridine and dimethyl sulfoxide was 14.8 g:28.4 g:9.2 mL:200 mL.

[0012] Pyridine is used as an acid-binding agent, and the molar ratio of intermediate 1 and 2,6-di-tert-butyl-4-bromomethylphenol is controlled to be 1.05-1.1:1. Then, -Br of 2,6-di-tert-butyl-4-bromomethylphenol and -NH- of intermediate 1 undergo a nucleophilic substitution reaction under heating. The reaction process is as follows:

[0013]

[0014] S3. At room temperature, the intermediate 2, 2-mercaptobenzimidazole, benzoin dimethyl ether and dimethyl sulfoxide were fully stirred until they were uniformly mixed, and then irradiated under a 365nm ultraviolet lamp for 15 minutes. After the reaction was completed, the auxiliary agent was obtained by distillation under reduced pressure; the amount ratio of the intermediate 2, 2-mercaptobenzimidazole, benzoin dimethyl ether and dimethyl sulfoxide was 30.9g:8.9g:0.44g:200mL.

[0015] Benzoin dimethyl ether is used as a photoinitiator, and the molar ratio of intermediate 2 and 2-mercaptobenzimidazole is controlled to be 1:1. Then, the carbon-carbon double bond of intermediate 2 and the -SH of 2-mercaptobenzimidazole undergo a thiol-ene click reaction. The reaction process is as follows:

[0016]

[0017] The auxiliary agent contains a hindered phenol structure and a benzimidazole structure, which can synergistically play the role of anti-oxidation, anti-corrosion and de-sedimentation, and prevent the formation and deposition of lead sulfate during the redox reaction of the battery. At the same time, the auxiliary agent contains multiple hydroxyl groups, which can produce hydrogen bond interactions with hydroxyl groups in phosphoric acid, fumed silica and deionized water, so the auxiliary agent has good compatibility with the remaining raw materials, can be uniformly dispersed and stably present in the electrolyte, and then produce stable and effective anti-oxidation, anti-corrosion and de-sedimentation effects. Therefore, adding the auxiliary agent of the present invention into the electrolyte can improve the charge and discharge performance of the battery and extend the service life of the battery.

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

[0019] A method for preparing a high-power lead-acid battery electrolyte comprises the following steps:

[0020] Weigh each raw material by weight, and then fully stir phosphoric acid, anhydrous sodium sulfate, stannous sulfate, lithium iodide, lithium carbonate and sulfuric acid until they are evenly mixed to obtain a premixed solution for use; then mix deionized water and fumed silica in a gel making machine, add isopropyl alcohol and acrylamide while stirring, mix well and then mix with the premixed solution, continue stirring and add a defoaming agent and an auxiliary agent, and after stirring well, a high-power lead-acid battery electrolyte can be prepared.

[0021] The beneficial effects of the present invention are as follows: the auxiliary agent contains a hindered phenol structure, a benzimidazole structure and a plurality of hydroxyl groups, so the auxiliary agent has good compatibility with other raw materials, and the auxiliary agent can be uniformly dispersed and stably present in the electrolyte, thereby producing stable and effective anti-oxidation, anti-corrosion and sediment removal effects. Therefore, adding the auxiliary agent of the present invention into the electrolyte can improve the charge and discharge performance of the battery and extend the service life of the battery. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Example 1

[0024] Preparation of auxiliary agent, the specific steps are as follows:

[0025] S1. Under nitrogen protection, 9.9 g of 3-amino-1,2-propanediol, 18.1 mL of triethylamine and 120 mL of ethanol were stirred until uniformly mixed, and then 10.1 mL of 4-chloro-1-butene was slowly added after the temperature was raised to 60°C. After the addition was completed, 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 at room temperature until they were uniformly mixed, and then 28.4 g of 2,6-di-tert-butyl-4-bromomethylphenol was slowly added after the temperature was raised to 80°C. After the addition was completed, 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 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, and then 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 they are uniformly mixed to obtain a premixed solution for use; then mix 40 parts of deionized water and 0.5 parts of fumed silica in a glue making machine, add 0.1 parts of isopropanol and 0.1 parts of acrylamide while stirring, mix well and then mix with the premixed solution, continue stirring and add 0.005 parts of glycerol polyoxypropylene polyoxyethylene ether and 0.02 parts of the auxiliary agent prepared in Example 1, and stir well to prepare a lead-acid battery electrolyte.

[0031] Example 3

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

[0033] Weigh each raw material by weight, and then stir 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 until they are evenly mixed to obtain a premixed solution for use; then mix 55 parts of deionized water and 1.2 parts of fumed silica in a glue making machine, add 0.2 parts of isopropanol and 0.15 parts of acrylamide while stirring, mix well and then mix with the premixed solution, continue stirring and add 0.008 parts of tributyl phosphate and 0.07 parts of the auxiliary agent prepared in Example 1, and stir well to obtain a lead-acid battery electrolyte.

[0034] Example 4

[0035] Prepare lead-acid battery electrolyte, the specific steps are as follows:

[0036] Weigh each raw material by weight, and then stir 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 until they are evenly mixed to obtain a premixed solution for use; then mix 60 parts of deionized water and 2 parts of fumed silica in a glue making machine, add 0.3 parts of isopropanol and 0.2 parts of acrylamide while stirring, mix well and then mix with the premixed solution, continue stirring and add 0.01 parts of glycerol polyoxypropylene polyoxyethylene ether and 0.1 parts of the auxiliary agent prepared in Example 1, and stir well to obtain a lead-acid battery electrolyte.

[0037] Comparative Example 1

[0038] Prepare lead-acid battery electrolyte, the specific steps are as follows:

[0039] The remaining steps remained unchanged, except that the auxiliary agent in Example 2 was replaced by 0.09 parts of antioxidant 264 and 0.01 parts of p-chlorobenzylbenzimidazole to prepare a lead-acid battery electrolyte.

[0040] Performance Testing

[0041] The lead-acid battery electrolytes prepared in Examples 2-4 and Comparative Example 1 were used in lead-acid batteries. After testing, the performance comparison with other lead-acid batteries using common electrolytes is shown in the following table:

[0042]

[0043] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation 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 contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

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 isopropanol, 0.1-0.2 parts of acrylamide, 0.02-0.1 parts of auxiliary agent and 0.005-0.01 parts of defoaming agent; Wherein, the auxiliary agent is prepared by the following steps: S1. Stir 3-amino-1,2-propanediol, triethylamine and ethanol under nitrogen protection, add 4-chloro-1-butene after heating to 60°C, react for 3h, cool, and distill under reduced pressure to obtain intermediate 1; S2, stirring intermediate 1, pyridine and dimethyl sulfoxide, heating to 80°C, adding 2,6-di-tert-butyl-4-bromomethylphenol, reacting for 5 hours, cooling, and distilling 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 365 nm ultraviolet lamp for 15 min, 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. A high-power lead-acid battery electrolyte according to claim 1, characterized in that: The usage ratio of the intermediate 1, 2,6-di-tert-butyl-4-bromomethylphenol, pyridine and dimethyl sulfoxide in step S2 is 14.8 g:28.4 g:9.2 mL:200 mL.

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

6. The method for preparing a high-power lead-acid battery electrolyte according to claim 1, characterized in that: The following steps are involved: Weigh each raw material by weight, and then fully stir phosphoric acid, anhydrous sodium sulfate, stannous sulfate, lithium iodide, lithium carbonate and sulfuric acid until they are evenly mixed to obtain a premixed solution for use; then mix deionized water and fumed silica in a gel making machine, add isopropyl alcohol and acrylamide while stirring, mix well and then mix with the premixed solution, continue stirring and add a defoaming agent and an auxiliary agent, and after stirring well, a high-power lead-acid battery electrolyte can be prepared.

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