阅读说明：本技术 一种长寿命胶体蓄电池用电解液及其制备方法 (Electrolyte for long-life colloid storage battery and preparation method thereof ) 是由 侯娜娃 张树祥 豆江洪 薛胜凡 张波 王金梅 于 2021-08-09 设计创作，主要内容包括：本发明提供了一种长寿命胶体蓄电池用电解液,所述电解液由质量分数为4％～6.5％的气相二氧化硅,35％～45％的硫酸溶液,0.5％～1％的无水硫酸钠、硫酸钾、硫酸锂混合物,0.5％～1.5％的磷酸,0.05％～0.15％的聚乙烯醇,0.05％～0.15％的甘油,0.05％～0.15％的硫酸亚锡和纯水组成。本发明优点在于,所配制的胶体电解液交联度高、稳定性好,同时,具有较强的触变性和流变性,由该胶体电解液所制得的电池较普通的胶体电池自放电低、耐高低温性能强,容量高且深循环性能优越。(The invention provides an electrolyte for a long-life colloid storage battery, which consists of 4-6.5% of fumed silica, 35-45% of sulfuric acid solution, 0.5-1% of anhydrous sodium sulfate, potassium sulfate and lithium sulfate mixture, 0.5-1.5% of phosphoric acid, 0.05-0.15% of polyvinyl alcohol, 0.05-0.15% of glycerol, 0.05-0.15% of stannous sulfate and pure water by mass fraction. The invention has the advantages that the prepared colloid electrolyte has high crosslinking degree and good stability, and simultaneously has stronger thixotropy and rheological property, and compared with the common colloid battery, the battery prepared by the colloid electrolyte has low self-discharge, strong high and low temperature resistance, high capacity and excellent deep cycle performance.)

1. The electrolyte for the long-life colloid storage battery is characterized in that: the electrolyte consists of 4 to 6.5 mass percent of fumed silica, 35 to 45 mass percent of sulfuric acid solution, 0.5 to 1 mass percent of anhydrous sodium sulfate, potassium sulfate and lithium sulfate mixture, 0.5 to 1.5 mass percent of phosphoric acid, 0.05 to 0.15 mass percent of polyvinyl alcohol, 0.05 to 0.15 mass percent of glycerol, 0.05 to 0.15 mass percent of stannous sulfate and pure water.

2. The long-life colloid storage battery electrolyte as set forth in claim 1, wherein: the fumed silica particle ratioArea of 200m²Per g, and the particle diameter requires D₅₀≤60nm，D_max≤120nm。

3. The long-life colloid storage battery electrolyte as set forth in claim 1, wherein: the temperature of the sulfuric acid solution is less than 10 ℃, and the density of the sulfuric acid solution is 1.290-1.320 g/cm³In the meantime.

4. The method for producing an electrolyte for a long-life colloid secondary battery as claimed in claim 1, wherein: the method comprises the following steps:

s1, confirming the temperature and density of the sulfuric acid solution required by the formula: the temperature is less than 10 ℃, and the density is 1.290-1.320 g/cm³To (c) to (d);

s2, calculating and weighing the required amounts of fumed silica, sulfuric acid solution, anhydrous sodium sulfate, potassium sulfate, lithium sulfate mixture, phosphoric acid, polyvinyl alcohol, glycerol, stannous sulfate and pure water according to the formula proportion of claim 1;

s3, adding the sulfuric acid solution weighed in the step S2, the anhydrous sodium sulfate, the potassium sulfate, the lithium sulfate mixture, the phosphoric acid, the polyvinyl alcohol, the glycerol, the stannous sulfate and the pure water into a stirring kettle, stirring and dissolving, and adding the amount of the fumed silica required by the formula under the stirring state.

5. The method for producing an electrolyte for a long-life colloid secondary battery as claimed in claim 4, wherein: the rotating speed of the stirring kettle is set to 3000r/min, and the stirring time is 15-30 min.

Technical Field

The invention relates to the technical field of colloid storage batteries, in particular to electrolyte for a long-life colloid storage battery and a preparation method thereof.

Background

In the case of a gel-sealed lead-acid battery, the silica gel molecules within the battery are connected to each other to form a three-dimensional porous network-like skeleton structure, which houses the electrolyte therein. After the electrolyte is filled into the battery, gel reaction can continuously occur in the charging process, at the moment, the framework is further dehydrated and contracted, so that cracks are formed in the system and penetrate between the positive plate and the negative plate, and a channel reaching the negative electrode is provided for oxygen separated out from the positive electrode, thereby realizing cathode absorption. Compared with the traditional storage battery, the colloid battery has the characteristics of strong high and low temperature resistance, low self-discharge, long cycle life and wide application environment range.

The electrolyte preparation process is one of core processes for manufacturing the gel battery, and the currently prepared gel still has the problems of hydration delamination in different degrees, poor thixotropic property, weak rheological property and low capacity.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides an electrolyte for a long-life colloid storage battery and a preparation method thereof.

The invention solves the technical problems through the following technical means:

the electrolyte for the long-life colloid storage battery consists of 4 to 6.5 mass percent of fumed silica, 35 to 45 mass percent of sulfuric acid solution, 0.5 to 1 mass percent of anhydrous sodium sulfate, potassium sulfate and lithium sulfate mixture, 0.5 to 1.5 mass percent of phosphoric acid, 0.05 to 0.15 mass percent of polyvinyl alcohol, 0.05 to 0.15 mass percent of glycerol, 0.05 to 0.15 mass percent of stannous sulfate and pure water.

Preferably, the fumed silica particles have a specific surface area of 200m²Per g, and the particle diameter requires D₅₀≤60nm，D_max≤120nm。

Preferably, the temperature of the sulfuric acid solution is less than 10 ℃, and the density of the sulfuric acid solution is 1.290-1.320 g/cm³In the meantime.

A preparation method of electrolyte for a long-life colloid storage battery comprises the following steps:

s1, confirming the temperature and density of the sulfuric acid solution required by the formula: the temperature is less than 10 ℃, and the density is 1.290-1.320 g/cm³To (c) to (d);

s2, calculating and weighing the required amounts of fumed silica, sulfuric acid solution, anhydrous sodium sulfate, potassium sulfate, lithium sulfate mixture, phosphoric acid, polyvinyl alcohol, glycerol, stannous sulfate and pure water according to the formula proportion of claim 1;

s3, adding the sulfuric acid solution weighed in the step S2, the anhydrous sodium sulfate, the potassium sulfate, the lithium sulfate mixture, the phosphoric acid, the polyvinyl alcohol, the glycerol, the stannous sulfate and the pure water into a stirring kettle, stirring and dissolving, and adding the amount of the fumed silica required by the formula under the stirring state.

Preferably, the rotating speed of the stirring kettle is set to 3000r/min, and the stirring time is 15-30 min.

The invention has the advantages that: the colloid electrolyte prepared by the invention has high crosslinking degree, good stability, and stronger thixotropy and rheological property, and compared with the common colloid battery, the battery prepared by the colloid electrolyte has low self-discharge, strong high and low temperature resistance, high capacity and excellent deep cycle performance.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Preparing an electrolyte for a long-life colloid storage battery, wherein the colloid storage battery comprises the following components in percentage by mass: 4 percent of fumed silica, 35 percent of sulfuric acid solution, 0.5 percent of anhydrous sodium sulfate, potassium sulfate and lithium sulfate mixture, 0.5 percent of phosphoric acid, 0.05 percent of polyvinyl alcohol, 0.05 percent of glycerol, 0.05 percent of stannous sulfate and the balance of pure water. Meanwhile, the particle diameter D of the fumed silica particles used in the present embodiment₅₀＝58nm，D_max110nm, and the density was measured at 10 ℃ in a sulfuric acid solution of 1.300g/cm³。。

Calculating and weighing the components of the materials required by the electrolyte of the colloidal storage battery: 40kg of fumed silica, 350kg of sulfuric acid solution, 5kg of anhydrous sodium sulfate, potassium sulfate and lithium sulfate mixture, 5kg of phosphoric acid, 0.5kg of polyvinyl alcohol, 0.5kg of glycerol, 0.5kg of stannous sulfate and 598.5kg of pure water.

And adding the weighed sulfuric acid solution, the anhydrous sodium sulfate, the potassium sulfate and the lithium sulfate mixture, phosphoric acid, polyvinyl alcohol, glycerol, stannous sulfate and pure water into a stirring kettle, stirring and dissolving, setting the rotating speed of the stirring kettle to be 3000r/min, adding fumed silica required by the formula under the stirring state, and continuously stirring for 15-30 min to obtain the colloidal electrolyte.

Example 2

Preparing an electrolyte for a long-life colloid storage battery, wherein the colloid storage battery comprises the following components in percentage by mass: 6.5 percent of fumed silica, 45 percent of sulfuric acid solution, 1 percent of anhydrous sodium sulfate, potassium sulfate and lithium sulfate mixture, 1.5 percent of phosphoric acid, 0.15 percent of polyvinyl alcohol, 0.15 percent of glycerol, 0.15 percent of stannous sulfate and the balance of pure water. Meanwhile, the particle diameter D of the fumed silica particles used in the present embodiment₅₀＝58nm，D_max110nm, and the density was measured at 10 ℃ in a sulfuric acid solution of 1.300g/cm³。。

Calculating and weighing the components of the materials required by the electrolyte of the colloidal storage battery: 65kg of fumed silica, 450kg of sulfuric acid solution, 10kg of anhydrous sodium sulfate, potassium sulfate and lithium sulfate mixture, 15kg of phosphoric acid, 1.5kg of polyvinyl alcohol, 1.5kg of glycerol, 1.5kg of stannous sulfate and 455.5kg of pure water.

And adding the weighed sulfuric acid solution, the anhydrous sodium sulfate, the potassium sulfate and the lithium sulfate mixture, phosphoric acid, polyvinyl alcohol, glycerol, stannous sulfate and pure water into a stirring kettle, stirring and dissolving, setting the rotating speed of the stirring kettle to be 3000r/min, adding fumed silica required by the formula under the stirring state, and continuously stirring for 15-30 min to obtain the colloidal electrolyte.

Example 3

Preparation of long-life colloid accumulatorThe electrolyte for the battery, wherein the colloid storage battery comprises the following components in percentage by mass: 5.25 percent of fumed silica, 40 percent of sulfuric acid solution, 0.75 percent of anhydrous sodium sulfate, potassium sulfate and lithium sulfate mixture, 1 percent of phosphoric acid, 0.1 percent of polyvinyl alcohol, 0.1 percent of glycerol, 0.1 percent of stannous sulfate and the balance of pure water. Meanwhile, the particle diameter D of the fumed silica particles used in the present embodiment₅₀＝58nm，D_max110nm, and the density was measured at 10 ℃ in a sulfuric acid solution of 1.300g/cm³。。

Calculating and weighing the components of the materials required by the electrolyte of the colloidal storage battery: 52.5kg fumed silica, 400kg sulfuric acid solution, 7.5kg anhydrous sodium sulfate, potassium sulfate, lithium sulfate mixture, 10kg phosphoric acid, 1kg polyvinyl alcohol, 1kg glycerin, 1kg stannous sulfate, 527kg pure water.

And adding the weighed sulfuric acid solution, the anhydrous sodium sulfate, the potassium sulfate and the lithium sulfate mixture, phosphoric acid, polyvinyl alcohol, glycerol, stannous sulfate and pure water into a stirring kettle, stirring and dissolving, setting the rotating speed of the stirring kettle to be 3000r/min, adding fumed silica required by the formula under the stirring state, and continuously stirring for 15-30 min to obtain the colloidal electrolyte.

The colloidal electrolyte prepared in the examples 1, 2 and 3 is poured into a battery (both positive and negative plates are pasted plates), the obtained sample battery is subjected to 25 ℃ normal temperature capacity, -18 ℃ low temperature capacity, capacity preservation rate and 100% DOD cycle life test (firstly, the battery with qualified 10h rate is fully charged, and is discharged to 10.8V/battery in the environment of 25 ℃ at 5.5A, secondly, 14.1V/battery is charged at constant voltage and current limited 8.25A for 16h, thirdly, standing for 2h, fourthly, the steps are repeated until the 10h rate discharge capacity is lower than 44 Ah), and the detection result is compared with the common colloidal battery with the same model as the following result:

the above comparative data show that: the sample battery prepared by the colloidal electrolyte has greatly improved normal temperature capacity, low temperature resistance and cycle service life, and simultaneously has low self-discharge.

It is noted that, in this document, relational terms such as first and second, and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.