CN109659630B - Preparation method of lead-acid storage battery colloidal electrolyte - Google Patents
Preparation method of lead-acid storage battery colloidal electrolyte Download PDFInfo
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- CN109659630B CN109659630B CN201811275252.XA CN201811275252A CN109659630B CN 109659630 B CN109659630 B CN 109659630B CN 201811275252 A CN201811275252 A CN 201811275252A CN 109659630 B CN109659630 B CN 109659630B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
- H01M10/10—Immobilising of electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to a lead-acid storage battery colloid electrolyte and a preparation method thereof, wherein the lead-acid storage battery colloid electrolyte comprises the following raw materials in parts by weight: 20-25 parts of water gel emulsion; 40-50 parts of concentrated sulfuric acid; 1-5 parts of phosphoric acid; boric acid: 0.5 to 2; sodium carboxymethylcellulose: 0.5 to 1; deionized water: 30-35; fumed silica 0.1-0.5; 0.1-0.5 of coagulant aid; in order to improve the service life of the baby carriage battery, the AGM battery is filled with colloidal electrolyte to prepare an AGM-colloidal mixed battery; the improved baby carriage battery structure solves the problems of low specific energy and high price of foreign colloid storage batteries, and provides a colloid electrolyte lead-acid storage battery which is made of a separator with excellent performance and low price and is suitable for colloid storage batteries.
Description
Technical Field
The invention relates to the technical field of storage batteries, in particular to a preparation method of a lead-acid storage battery colloidal electrolyte.
Background
The lead-acid storage battery has the characteristics of easily available raw materials, simple manufacture, stable performance, low price, complete varieties and the like, and still occupies the domination in various secondary chemical power sources so far and occupies the largest market share. The valve-regulated sealed battery includes two types, an adsorption type battery and a gel electrolyte battery. The former uses superfine glass fiber separator (AGM) to adsorb dilute sulfuric acid electrolyte, and the battery has small internal resistance, relatively low electrolyte content and excellent heavy current discharge performance, and is suitable for use as starting battery and various emergency power supply (UPS). The AGM battery is a poor liquid type, electrolyte stratification can occur in charging and discharging, floating charging current is large, heat generation is high, heat dissipation is poor, the AGM battery is not suitable for deep discharge cycle use, bulging and thermal runaway phenomena are easy to occur, and the use conditions are limited. The gel accumulator is prepared by adding SiO2 gel into dilute sulfuric acid to make the electrolyte gel and lose fluidity, so that the battery has no leakage and no electrolyte stratification. The colloid accumulator has slightly high internal resistance, 10% lower specific energy, complicated production process and high material cost, so that the colloid accumulator has much higher selling price than conventional accumulator and AGM accumulator.
In view of the above problems, it is necessary to improve them.
SUMMERY OF THE UTILITY MODEL
The invention aims to overcome the defects in the prior art and improve the existing lead-acid storage battery colloidal electrolyte, and the invention also aims to provide the lead-acid storage battery colloidal electrolyte and a preparation method thereof.
In order to achieve the purpose of the utility model, the invention adopts the following technical scheme: the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 20-25 parts of water gel emulsion; 40-50 parts of concentrated sulfuric acid; 1-5 parts of phosphoric acid; boric acid: 0.5 to 2; sodium carboxymethylcellulose: 0.5 to 1; deionized water: 30-35; fumed silica 0.1-0.5; 0.1-0.5 of coagulant aid.
As a preferred scheme of the invention, the lead-acid storage battery gel electrolyte comprises the following raw materials in parts by weight: 25 parts of water gel emulsion; 43 parts of concentrated sulfuric acid; 5 parts of phosphoric acid; boric acid: 0.5; sodium carboxymethylcellulose: 0.5; deionized water: 30, of a nitrogen-containing gas; fumed silica 0.1; and (5) a coagulant aid 0.2.
In a preferable embodiment of the invention, the aqueous gel emulsion is a mixture of silica and water, wherein the silica and water are mixed in a ratio of 1: 9.
In a preferred embodiment of the invention, the coagulant aid is a metal-organic framework formed by a metal salt hydrate and an organic carboxylic acid ligand.
As a preferred embodiment of the invention, the metal salt hydrate is copper nitrate trihydrate, and the organic carboxylic acid ligand is a ternary or quaternary carboxylic acid ligand, so as to form a metal-organic framework coagulant aid; the molar ratio of the metal salt hydrate to the organic carboxylic acid ligand is 0.5: 1-5.
A preparation method of lead-acid storage battery colloidal electrolyte comprises the following steps:
(1) cleaning the acid preparation tank and tools with pure water;
(2) adding the water latex solution with the proportion into an acid preparation tank to obtain solution A;
(3) the preparation of the sodium carboxymethyl cellulose solution comprises the following steps: mixing a certain amount of sodium carboxymethylcellulose and deionized water, and stirring at room temperature for 11h to obtain a solution with a concentration of 0.22 wt%; adding the proportioned sodium carboxymethylcellulose solution into the solution A, and uniformly stirring to obtain a solution B;
(4) slowly adding the concentrated sulfuric acid with the proportion into the solution B, and continuously stirring to obtain a solution C;
(5) adding fumed silica and the coagulant aid into the solution C while stirring, and continuously stirring uniformly after the addition is finished to obtain a solution D;
(6) adding the prepared solution D into a low-speed stirrer, stirring for 45-60 min, and stopping stirring to obtain a solution E;
(7) mixing the solution E with deionized water, and uniformly stirring to obtain a solution F;
(8) adding phosphoric acid and boric acid in proportion into the solution F, and uniformly mixing to obtain a solution G;
(9) adding the solution G into an acid storage tank, and pumping the solution G into an acid adding machine by using an acid-resistant pump; and preparing the obtained lead-acid storage battery colloidal electrolyte.
As a preferable proposal of the invention, during the step (9), a low-speed stirrer is arranged on the acid storage tank.
And (3) as a preferable scheme of the invention, in the step (9), a filter screen of 40-80 meshes is arranged at the corresponding position of the acid storage tank, and the solution G is filtered.
In a preferred embodiment of the invention, the concentrated sulfuric acid has a mass concentration of 90wt% or more.
The beneficial effects of the invention are as follows:
1. in order to improve the service life of the baby carriage battery, the AGM battery is filled with colloid electrolyte to prepare the AGM-colloid hybrid battery. The improved baby carriage battery structure solves the problems of low specific energy and high price of foreign colloid storage batteries, and provides a colloid electrolyte lead-acid storage battery which is made of a separator with excellent performance and low price and is suitable for colloid storage batteries.
2. The electrolyte of the invention takes the hydrogel emulsion and the sulfuric acid as solvents, the boric acid as a solute and the sodium carboxymethyl cellulose and the phosphoric acid as additives, on the basis of improving the formation efficiency and the fire dissipation voltage, the solubility of the solute is increased, the conductivity is improved, and the specific resistance is reduced, so that the service life of the product is prolonged, the growth speed of an oxide film is increased, the hydration of the oxide film is inhibited, the high-low temperature performance of the electrolyte is improved, the formation efficiency of the storage battery is improved, and the discharge efficiency is high.
Detailed Description
The invention will be described in detail with reference to the following examples.
Example 1: the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 25 parts of water gel emulsion; 43 parts of concentrated sulfuric acid; 5 parts of phosphoric acid; boric acid: 0.5; sodium carboxymethylcellulose: 0.5; deionized water: 30, of a nitrogen-containing gas; fumed silica 0.1; and (5) a coagulant aid 0.2.
The water gel emulsion is a mixture of silicon dioxide and water, wherein the silicon dioxide and the water are mixed according to the proportion of 1: 9.
The coagulant aid is a metal organic framework formed by a metal salt hydrate and an organic carboxylic acid ligand.
The metal salt hydrate is copper nitrate trihydrate, and the organic carboxylic acid ligand is ternary or quaternary carboxylic acid ligand, so that the metal organic framework coagulant aid is formed; the molar ratio of the metal salt hydrate to the organic carboxylic acid ligand is 0.5: 1-5.
A preparation method of lead-acid storage battery colloidal electrolyte comprises the following steps:
(1) cleaning the acid preparation tank and tools with pure water;
(2) adding the water latex liquid into an acid preparation tank according to the proportion, and adding Na2SO4 and SnSO4 according to the proportion; obtaining a solution A;
(3) the preparation of the sodium carboxymethyl cellulose solution comprises the following steps: mixing a certain amount of sodium carboxymethylcellulose and deionized water, and stirring at room temperature for 11h to obtain a solution with a concentration of 0.22 wt%; adding the proportioned sodium carboxymethylcellulose solution into the solution A, and uniformly stirring to obtain a solution B;
(4) slowly adding the concentrated sulfuric acid with the proportion into the solution B, and continuously stirring to obtain a solution C;
(5) adding fumed silica and the coagulant aid into the solution C while stirring, and continuously stirring uniformly after the addition is finished to obtain a solution D; adding a certain amount of fumed silica and a small amount of coagulant aid into the solution C with a certain proportion, and stirring and then pouring into a battery, wherein the advantages are represented by good dispersibility of the electrolyte, so that excellent properties of the fumed silica such as good thixotropy, fluidity and thickening property can be fully released; the stability of the electrolyte is good;
(6) adding the prepared solution D into a low-speed stirrer, stirring for 45-60 min, and stopping stirring to obtain a solution E;
(7) mixing the solution E with deionized water, and uniformly stirring to obtain a solution F;
(8) adding phosphoric acid and boric acid in proportion into the solution F, and uniformly mixing to obtain a solution G;
(9) adding the solution G into an acid storage tank, and pumping the solution G into an acid adding machine by using an acid-resistant pump; and preparing the obtained lead-acid storage battery colloidal electrolyte.
And (4) in the step (9), a low-speed stirrer is arranged on the acid storage tank.
And (4) in the step (9), a filter screen of 40-80 meshes is arranged at the corresponding position of the acid storage tank, and the solution G is filtered.
The mass concentration of the concentrated sulfuric acid is more than 90 wt%.
Example 2:
the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 23 parts of water gel emulsion; 45 parts of concentrated sulfuric acid; 3 parts of phosphoric acid; boric acid: 0.8; sodium carboxymethylcellulose: 0.6; deionized water: 32, a first step of removing the first layer; fumed silica 0.2; and (5) a coagulant aid 0.3.
The rest of this example refers to example 1, which is prepared in the same way as example 1.
Example 3:
the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 23 parts of water gel emulsion; 45 parts of concentrated sulfuric acid; 3 parts of phosphoric acid; boric acid: 0.8; sodium carboxymethylcellulose: 0.6; deionized water: 32, a first step of removing the first layer; fumed silica 0.45; and (5) a coagulant aid 0.3.
In the embodiment, on the basis of the embodiment 2, the weight ratio of the fumed silica is increased from 0.2 to 0.45, so that the excellent properties of the fumed silica, such as good thixotropy, fluidity and thickening property, are fully released; the stability of the electrolyte is good, and the produced electrolyte does not have the phenomena of sedimentation, flocculation and layering for a long time; can reduce the corrosion of the grid and inhibit water loss, and has good effects of large-current charging and discharging and small self-discharging of the storage battery.
The rest of this example refers to example 1, which is prepared in the same way as example 1.
Example 4:
the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 25 parts of water gel emulsion; 50 parts of concentrated sulfuric acid; 5 parts of phosphoric acid; boric acid: 0.5; sodium carboxymethylcellulose: 1; deionized water: 35; fumed silica 0.5; and (5) a coagulant aid 0.5.
The rest of this example refers to example 1, which is prepared in the same way as example 1.
Example 5:
the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 21 parts of water gel emulsion; 44 parts of concentrated sulfuric acid; 3 parts of phosphoric acid; boric acid: 0.8; sodium carboxymethylcellulose: 0.5; deionized water: 30, of a nitrogen-containing gas; fumed silica 0.25; and (5) a coagulant aid 0.45.
The rest of this example refers to example 1, which is prepared in the same way as example 1.
Example 6:
the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 21 parts of water gel emulsion; 44 parts of concentrated sulfuric acid; 3 parts of phosphoric acid; boric acid: 2; sodium carboxymethylcellulose: 0.5; deionized water: 30, of a nitrogen-containing gas; fumed silica 0.25; and (5) a coagulant aid 0.45.
In the embodiment, on the basis of the embodiment 5, the weight ratio of the phosphoric acid is increased from 3 to 4, and the weight ratio of the boric acid is increased from 0.8 to 1.5, so that the electrolyte increases the solubility of solute, improves the conductivity and reduces the specific resistance on the basis of improving the formation efficiency and the fire-spreading voltage, thereby prolonging the service life of the product and increasing the growth speed of an oxide film.
The rest of this example refers to example 1, which is prepared in the same way as example 1.
Example 7:
the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 20 parts of water gel emulsion; 40 parts of concentrated sulfuric acid; 1 part of phosphoric acid; boric acid: 0.5; sodium carboxymethylcellulose: 0.5; deionized water: 30, of a nitrogen-containing gas; fumed silica 0.1; and (5) a coagulant aid 0.1.
The rest of this example refers to example 1, which is prepared in the same way as example 1.
Example 8:
the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 22 parts of water gel emulsion; 45 parts of concentrated sulfuric acid; 2 parts of phosphoric acid; boric acid: 1; sodium carboxymethylcellulose: 0.8; deionized water: 33; fumed silica 0.25; and (5) a coagulant aid of 0.75.
The rest of this example refers to example 1, which is prepared in the same way as example 1.
Example 9:
the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 24 parts of water gel emulsion; 45 parts of concentrated sulfuric acid; 2 parts of phosphoric acid; boric acid: 1; sodium carboxymethylcellulose: 0.8; deionized water: 33; fumed silica 0.35; and (5) a coagulant aid 0.65.
The rest of this example refers to example 1, which is prepared in the same way as example 1.
Example 10:
the lead-acid storage battery colloidal electrolyte comprises the following raw materials in parts by weight: 22.5 parts of water gel emulsion; 40 parts of concentrated sulfuric acid; 1 part of phosphoric acid; boric acid: 0.5; sodium carboxymethylcellulose: 0.5; deionized water: 33.5; fumed silica 0.1; and (5) a coagulant aid 0.1.
The rest of this example refers to example 1, which is prepared in the same way as example 1.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention; thus, the invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The preparation method of the lead-acid storage battery colloid electrolyte is characterized by comprising the following steps: comprises the following raw materials in parts by weight: 20-25 parts of water gel emulsion; 40-50 parts of concentrated sulfuric acid; 1-5 parts of phosphoric acid; boric acid: 0.5 to 2; sodium carboxymethylcellulose: 0.5 to 1; deionized water: 30-35; fumed silica 0.1-0.5; 0.1-0.5 of coagulant aid; a preparation method of lead-acid storage battery colloidal electrolyte comprises the following steps:
(1) cleaning the acid preparation tank and tools with pure water;
(2) adding the water latex liquid into an acid preparation tank according to the proportion; obtaining a solution A;
(3) the preparation of the sodium carboxymethyl cellulose solution comprises the following steps: mixing a certain amount of sodium carboxymethylcellulose and deionized water, and stirring at room temperature for 11h to obtain a solution with a concentration of 0.22 wt%; adding the proportioned sodium carboxymethylcellulose solution into the solution A, and uniformly stirring to obtain a solution B;
(4) slowly adding the concentrated sulfuric acid with the proportion into the solution B, and continuously stirring to obtain a solution C;
(5) adding fumed silica and the coagulant aid into the solution C while stirring, and continuously stirring uniformly after the addition is finished to obtain a solution D;
(6) adding the prepared solution D into a low-speed stirrer, stirring for 45-60 min, and stopping stirring to obtain a solution E;
(7) mixing the solution E with deionized water, and uniformly stirring to obtain a solution F;
(8) adding phosphoric acid and boric acid in proportion into the solution F, and uniformly mixing to obtain a solution G;
(9) adding the solution G into an acid storage tank, and pumping the solution G into an acid adding machine by using an acid-resistant pump; and preparing the obtained lead-acid storage battery colloidal electrolyte.
2. The preparation method of the lead-acid storage battery colloidal electrolyte according to claim 1, characterized by comprising the following steps: comprises the following raw materials in parts by weight: 25 parts of water gel emulsion; 43 parts of concentrated sulfuric acid; 5 parts of phosphoric acid; boric acid: 0.5; sodium carboxymethylcellulose: 0.5; deionized water: 30, of a nitrogen-containing gas; fumed silica 0.1; and (5) a coagulant aid 0.2.
3. The preparation method of the lead-acid storage battery colloidal electrolyte according to claim 1 or 2, characterized by comprising the following steps: the water gel emulsion is a mixture of silicon dioxide and water, wherein the silicon dioxide and the water are mixed according to a ratio of 1: 9.
4. The preparation method of the lead-acid storage battery colloidal electrolyte according to claim 1 or 2, characterized by comprising the following steps: the coagulant aid is a metal organic framework formed by a metal salt hydrate and an organic carboxylic acid ligand.
5. The method for preparing the lead-acid storage battery colloidal electrolyte according to claim 4, characterized by comprising the following steps: the metal salt hydrate is copper nitrate trihydrate, and the organic carboxylic acid ligand is ternary or quaternary carboxylic acid ligand, so that the metal organic framework coagulant aid is formed; the molar ratio of the metal salt hydrate to the organic carboxylic acid ligand is 0.5: 1-5.
6. The method for preparing the lead-acid storage battery colloidal electrolyte according to the claim 1, wherein during the step (9), a low-speed stirrer is arranged on an acid storage tank.
7. The preparation method of the lead-acid storage battery colloidal electrolyte according to claim 1, wherein in the step (9), a filter screen of 40-80 meshes is installed at a corresponding position of the acid storage tank, and the solution G is filtered.
8. The method for preparing the colloidal electrolyte of the lead-acid storage battery according to claim 1, wherein the mass concentration of the concentrated sulfuric acid is more than 90 wt%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05121090A (en) * | 1991-10-25 | 1993-05-18 | Wan Riankisan | Large-capacity colloidal storage battery, colloidal electrolyte used for said storage battery and manufacture thereof |
| CN105514503A (en) * | 2016-02-03 | 2016-04-20 | 广东猛狮新能源科技股份有限公司 | Colloidal electrolyte of lead acid storage battery, and preparation method for colloidal electrolyte |
| CN107403965A (en) * | 2017-09-20 | 2017-11-28 | 吉林省凯禹电化学储能技术发展有限公司 | A kind of energy storage lead-acid battery electrolyte and preparation method thereof |
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2018
- 2018-10-30 CN CN201811275252.XA patent/CN109659630B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05121090A (en) * | 1991-10-25 | 1993-05-18 | Wan Riankisan | Large-capacity colloidal storage battery, colloidal electrolyte used for said storage battery and manufacture thereof |
| CN105514503A (en) * | 2016-02-03 | 2016-04-20 | 广东猛狮新能源科技股份有限公司 | Colloidal electrolyte of lead acid storage battery, and preparation method for colloidal electrolyte |
| CN107403965A (en) * | 2017-09-20 | 2017-11-28 | 吉林省凯禹电化学储能技术发展有限公司 | A kind of energy storage lead-acid battery electrolyte and preparation method thereof |
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