CN103441308B - A kind of lead-acid accumulator electrolyte and preparation method thereof and lead acid accumulator - Google Patents
A kind of lead-acid accumulator electrolyte and preparation method thereof and lead acid accumulator Download PDFInfo
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Abstract
The invention discloses a kind of lead-acid accumulator electrolyte and preparation method thereof and lead acid accumulator, comprise sulfuric acid, nano fumed silica, potassium sulfate, zinc sulfate, ammonium sulfate, magnesium sulfate, aluminum sulfate, sodium sulphate, nickelous sulfate, cobaltous sulfate, lead sulfate, lithium iodide, CMC, polyvinyl alcohol, polyglycol ether, sodium ethylene diamine tetracetate and deionized water.The present invention can solve the deficiencies in the prior art, can significantly improve the access times of lead acid accumulator, is easy to promote the use of.
Description
Technical field
The present invention relates to Lead-acid Battery Technology field, especially a kind of lead-acid accumulator electrolyte and preparation method thereof and lead acid accumulator.
Background technology
Lead acid accumulator by since invention, has had the history of more than 100 year from 1958 so far.Lead acid accumulator has that structure is simple, dependable performance, easy to use, raw material are easy to get and the advantage such as low price, be widely used in the various fields in the national economy such as communications and transportation, communication and national defence, become indispensable energy products in social production and human lives.
Five large parts of lead acid accumulator are positive pole, negative pole, barrier film, electrolyte and battery case, and wherein electrolyte is one of principal element affecting battery performance.Common electrolyte internal resistance is large, Gu sour ability, useful life are short.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of lead-acid accumulator electrolyte and preparation method thereof and lead acid accumulator, can significantly improve the access times of lead acid accumulator, is easy to promote the use of.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows.
A kind of lead-acid accumulator electrolyte, comprises
The sulfuric acid of 48wt% ~ 50wt%,
The nano fumed silica of 0.3wt% ~ 0.5wt%,
The potassium sulfate of 0.1wt% ~ 0.3wt%,
The zinc sulfate of 0.1wt% ~ 0.3wt%,
The ammonium sulfate of 0.07wt% ~ 0.2wt%,
The magnesium sulfate of 0.2wt% ~ 0.5wt%,
The aluminum sulfate of 0.4wt% ~ 0.7wt%,
The sodium sulphate of 0.5wt% ~ 1.0wt%,
The nickelous sulfate of 0.1wt% ~ 0.2wt%,
The cobaltous sulfate of 0.02wt% ~ 0.08wt%,
The lead sulfate of 0.3wt% ~ 0.5wt%,
The lithium iodide of 0.05wt% ~ 0.2wt%,
The CMC of 0.2wt% ~ 0.4wt%,
The polyvinyl alcohol of 0.3wt% ~ 0.5wt%,
The polyglycol ether of 0.4wt% ~ 0.6wt%,
The sodium ethylene diamine tetracetate of 0.3wt% ~ 0.7wt%,
Surplus is deionized water.
A preparation method for lead-acid accumulator electrolyte, comprises the following steps:
A, the sulfuric acid of 48wt% ~ 50wt% slowly to be poured in deionized water, and at the uniform velocity stir with the speed of 5 ~ 10r/min, heat is volatilized fast, the temperature of sulfuric acid solution is down to < 50 DEG C;
B, the potassium sulfate of 0.1wt% ~ 0.3wt% is put in the sulfuric acid solution prepared in above-mentioned steps A, the zinc sulfate of 0.1wt% ~ 0.3wt%, the ammonium sulfate of 0.07wt% ~ 0.2wt%, the magnesium sulfate of 0.2wt% ~ 0.5wt%, the aluminum sulfate of 0.4wt% ~ 0.7wt%, the sodium sulphate of 0.5wt% ~ 1.0wt%, the nickelous sulfate of 0.1wt% ~ 0.2wt%, the cobaltous sulfate of 0.02wt% ~ 0.08wt%, the lead sulfate of 0.3wt% ~ 0.5wt%, the lithium iodide of 0.05wt% ~ 0.2wt%, stir, the temperature of mixed solution is made to be down to < 40 DEG C,
The CMC of 0.2wt% ~ 0.4wt% is added in C, the mixed solution prepared in above-mentioned steps B, the polyvinyl alcohol of 0.3wt% ~ 0.5wt%, the polyglycol ether of 0.4wt% ~ 0.6wt%, the sodium ethylene diamine tetracetate of 0.3wt% ~ 0.7wt%, stir, make the temperature of mixed solution be down to < 30 DEG C;
Add the nano fumed silica of 0.3wt% ~ 0.5wt% in D, the mixed solution prepared in above-mentioned steps C, stir, make the temperature of mixed solution be down to room temperature, obtain lead-acid accumulator electrolyte.
As a kind of optimal technical scheme of this preparation method, deionization resistivity of water >=18M Ω.
As a kind of optimal technical scheme of this preparation method, the purity of sulfuric acid is for analyzing pure rank.
As a kind of optimal technical scheme of this preparation method, the particle diameter of nano fumed silica is 50nm ~ 80nm, specific area > 200 ㎡/g.
A kind of lead acid accumulator, the lead-acid accumulator electrolyte comprising above-mentioned lead-acid accumulator electrolyte or prepare according to the preparation method of above-mentioned lead-acid accumulator electrolyte.
The beneficial effect adopting technique scheme to bring is: the present invention adopts CMC to form colloidal electrolyte of lead acid accumulator, described CMC is a kind of nonionic surface active agent, it has stronger water holding capacity and good flow adjustment, effectively can reduce the loss of electrolyte moisture in battery use procedure, thus improve the cycle life of lead acid accumulator.The content of described CMC controls as 0.2wt% ~ 0.4wt% by the present invention, can improve the performance of electrolyte preferably.Experiment shows, colloidal electrolyte of lead acid accumulator provided by the invention makes the cycle life of lead acid accumulator be at least 560 times, and namely lead acid accumulator has good cycle life.In addition, described CMC has excellent thickening, bonding, emulsification and peptizaiton; Described CMC dissolves in hot water or cold water, do not precipitate at high temperature or when boiling, having large-scale dissolubility, viscosity characteristics and non-thermal gelation, can coexist with multiple waterborne polymeric, surfactant and salt, is a kind of excellent colloidal thickener containing high concentration electrolyte solution; And it has the effect of good protecting colloid, make the present invention adopt a small amount of silicon dioxide can obtain stable colloidal electrolyte, be not only beneficial to the application of colloidal electrolyte, and can save production cost.Moreover preparation method's technique of colloidal electrolyte of lead acid accumulator provided by the invention is simple, and cost is lower, is suitable for suitability for industrialized production.
Ammonium sulfate, magnesium sulfate and sodium ethylene diamine tetracetate form deoxidier jointly, in the use procedure of lead acid accumulator, the reasons such as the dehydration that the impacts such as pole plate is put owing to overcharging, excessively, temperature cause or sulfuration, acidification phenomenon can be formed, cause lead oxide to come off, pole plate is loose, poor activity, the deoxidation of this deoxidier assists lead sulfate particle to decompose fast and reduction.The moisture in electrolyte can be supplemented, solve mistake water problem, pH value be adjusted in optimum state simultaneously.
Nanometer grade silica has good thixotropy, mobility and thickening property.
Polyvinyl alcohol can with metal ion-chelant, increase active material utilization.Polyglycol ether can improve nanometer grade silica dispersiveness in the electrolytic solution, makes electrolyte more stable, alleviates the vibrations that battery is subject to well.
Nickelous sulfate, cobaltous sulfate and lithium iodide, as stabilizer, reduce the self-discharge rate of storage battery; Decrease the dehydration of storage battery; High temperature, cryogenic property improve; There is the ability to accept of resistance to charging, saturated charging, improve charge acceptance; Improve the service life cycle of storage battery.
Embodiment
A kind of lead-acid accumulator electrolyte, comprises
The sulfuric acid of 49.75wt%,
The nano fumed silica of 0.46wt%,
The potassium sulfate of 0.13wt%,
The zinc sulfate of 0.20wt%,
The ammonium sulfate of 0.10wt%,
The magnesium sulfate of 0.45wt%,
The aluminum sulfate of 0.58wt%,
The sodium sulphate of 0.85wt%,
The nickelous sulfate of 0.15wt%,
The cobaltous sulfate of 0.05wt%,
The lead sulfate of 0.48wt%,
The lithium iodide of 0.11wt%,
The CMC of 0.26wt%,
The polyvinyl alcohol of 0.41wt%,
The polyglycol ether of 0.53wt%,
The sodium ethylene diamine tetracetate of 0.35wt%,
Surplus is deionized water.
A preparation method for lead-acid accumulator electrolyte, is characterized in that comprising the following steps:
A, the sulfuric acid of 49.75wt% slowly to be poured in deionized water, and at the uniform velocity stir with the speed of 5 ~ 10r/min, heat is volatilized fast, the temperature of sulfuric acid solution is down to < 50 DEG C;
The potassium sulfate of 0.13wt% is put in B, the sulfuric acid solution prepared in above-mentioned steps A, the zinc sulfate of 0.20wt%, the ammonium sulfate of 0.10wt%, the magnesium sulfate of 0.45wt%, the aluminum sulfate of 0.58wt%, the sodium sulphate of 0.85wt%, the nickelous sulfate of 0.15wt%, the cobaltous sulfate of 0.05wt%, the lead sulfate of 0.48wt%, the lithium iodide of 0.11wt%, stirs, and makes the temperature of mixed solution be down to < 40 DEG C;
The CMC of 0.26wt% is added in C, the mixed solution prepared in above-mentioned steps B, the polyvinyl alcohol of 0.41wt%, the polyglycol ether of 0.53wt%, the sodium ethylene diamine tetracetate of 0.35wt%, stir, make the temperature of mixed solution be down to < 30 DEG C;
Add the nano fumed silica of 0.46wt% in D, the mixed solution prepared in above-mentioned steps C, stir, make the temperature of mixed solution be down to room temperature, obtain lead-acid accumulator electrolyte.
It should be noted that deionization resistivity of water >=18M Ω.
It should be noted that the purity of sulfuric acid is for analyzing pure rank.
In addition, the particle diameter of nano fumed silica is 50nm ~ 80nm, specific area > 200 ㎡/g.
The present embodiment additionally provides a kind of lead acid accumulator, the lead-acid accumulator electrolyte comprising above-mentioned lead-acid accumulator electrolyte or prepare according to the preparation method of above-mentioned lead-acid accumulator electrolyte.After obtaining lead-acid accumulator electrolyte, utilize acid filling machine to be injected in battery, obtain lead acid accumulator.
Test according to CNS GB/T22473-2008 " energy storage lead acid accumulator ".Test result shows, gained lead acid accumulator has good charging and discharging capabilities, and its cycle life is more than 560 times.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. a lead-acid accumulator electrolyte, is characterized in that: comprise
The sulfuric acid of 48wt% ~ 50wt%,
The nano fumed silica of 0.3wt% ~ 0.5wt%,
The potassium sulfate of 0.1wt% ~ 0.3wt%,
The zinc sulfate of 0.1wt% ~ 0.3wt%,
The ammonium sulfate of 0.07wt% ~ 0.2wt%,
The magnesium sulfate of 0.2wt% ~ 0.5wt%,
The aluminum sulfate of 0.4wt% ~ 0.7wt%,
The sodium sulphate of 0.5wt% ~ 1.0wt%,
The nickelous sulfate of 0.1wt% ~ 0.2wt%,
The cobaltous sulfate of 0.02wt% ~ 0.08wt%,
The lead sulfate of 0.3wt% ~ 0.5wt%,
The lithium iodide of 0.05wt% ~ 0.2wt%,
The CMC of 0.2wt% ~ 0.4wt%,
The polyvinyl alcohol of 0.3wt% ~ 0.5wt%,
The polyglycol ether of 0.4wt% ~ 0.6wt%,
The sodium ethylene diamine tetracetate of 0.3wt% ~ 0.7wt%,
Surplus is deionized water.
2. a preparation method for lead-acid accumulator electrolyte, is characterized in that comprising the following steps:
A, the sulfuric acid of 48wt% ~ 50wt% slowly to be poured in deionized water, and at the uniform velocity stir with the speed of 5 ~ 10r/min, heat is volatilized fast, the temperature of sulfuric acid solution is down to < 50 DEG C;
The potassium sulfate of 0.1wt% ~ 0.3wt% is put in B, the sulfuric acid solution prepared in above-mentioned steps A, the zinc sulfate of 0.1wt% ~ 0.3wt%, the ammonium sulfate of 0.07wt% ~ 0.2wt%, the magnesium sulfate of 0.2wt% ~ 0.5wt%, the aluminum sulfate of 0.4wt% ~ 0.7wt%, the sodium sulphate of 0.5wt% ~ 1.0wt%, the nickelous sulfate of 0.1wt% ~ 0.2wt%, the cobaltous sulfate of 0.02wt% ~ 0.08wt%, the lead sulfate of 0.3wt% ~ 0.5wt%, the lithium iodide of 0.05wt% ~ 0.2wt%, stirs, and makes the temperature of mixed solution be down to < 40 DEG C;
The CMC of 0.2wt% ~ 0.4wt% is added in C, the mixed solution prepared in above-mentioned steps B, the polyvinyl alcohol of 0.3wt% ~ 0.5wt%, the polyglycol ether of 0.4wt% ~ 0.6wt%, the sodium ethylene diamine tetracetate of 0.3wt% ~ 0.7wt%, stir, make the temperature of mixed solution be down to < 30 DEG C;
Add the nano fumed silica of 0.3wt% ~ 0.5wt% in D, the mixed solution prepared in above-mentioned steps C, stir, make the temperature of mixed solution be down to room temperature, obtain lead-acid accumulator electrolyte.
3. the preparation method of lead-acid accumulator electrolyte according to claim 2, is characterized in that: in steps A, deionization resistivity of water >=18M Ω.
4. the preparation method of lead-acid accumulator electrolyte according to claim 2, is characterized in that: in steps A, and the purity of sulfuric acid is for analyzing pure rank.
5. the preparation method of lead-acid accumulator electrolyte according to claim 2, is characterized in that: in step D, and the particle diameter of nano fumed silica is 50nm ~ 80nm, specific area > 200 ㎡/g.
6. a lead acid accumulator, is characterized in that: the lead-acid accumulator electrolyte that the preparation method comprising lead-acid accumulator electrolyte according to claim 1 or the lead-acid accumulator electrolyte according to claim 2 ~ 5 any one prepares.
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| CN104779414B (en) * | 2015-04-18 | 2017-02-01 | 浙江平湖华龙实业股份有限公司 | Lead-acid storage battery electrolyte and storage battery |
| CN105355984A (en) * | 2015-09-28 | 2016-02-24 | 芜湖日升重型机床有限公司 | Battery electrolyte for numerical control machine tool and preparation method of battery electrolyte and battery |
| CN106678721A (en) * | 2016-12-31 | 2017-05-17 | 新昌县迪斯曼科技有限公司 | Night lighting device for farmland |
| CN108258328B (en) * | 2017-11-13 | 2020-04-10 | 天能集团（河南）能源科技有限公司 | Preparation method of lead-acid storage battery colloidal electrolyte |
| CN109546232B (en) * | 2018-11-02 | 2021-11-05 | 小洋电源股份有限公司 | Solid-state silica gel traction storage battery |
| CN114094202A (en) * | 2021-10-28 | 2022-02-25 | 天能电池集团股份有限公司 | Electrolyte for valve-regulated lead storage battery and lead storage battery |
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