CN104091968A

CN104091968A - Gel electrolyte capable of prolonging service life of lead-acid battery

Info

Publication number: CN104091968A
Application number: CN201410372645.8A
Authority: CN
Inventors: 张慧; 方明学; 王斌; 张丽芳
Original assignee: Zhejiang Tianneng Battery Jiangsu New Energy Co Ltd
Current assignee: Zhejiang Tianneng Battery Jiangsu New Energy Co Ltd
Priority date: 2014-07-31
Filing date: 2014-07-31
Publication date: 2014-10-08

Abstract

The invention discloses gel electrolyte capable of prolonging the service life of a lead-acid battery. The gel electrolyte contains the following raw materials in percentage by weight: 0.1 to 0.5 percent of polyethylene glycol, 0.1 to 1 percent of stannous sulfate, 0.5 to 1.5 percent of sodium sulfate, 0.5 to 1 percent of phosphoric acid, 0.05 to 2 percent of an organic silicon polymer, 0.5 to 8 percent of fumed silica, 35 to 45 percent of sulfuric acid and the balance being de-ionized water. According to the gel electrolyte, the polyethylene glycol is used as a colloid stabilizer and can prevent colloids from being gelled or agglomerated before being filled into the battery and enhance the stability of the colloids to form a stable three-dimensional mesh structure; the stannous sulfate can be oxidized into stannic tin to improve the electrical conductivity of an active substance and the recharging capability of the battery which is discharged; the sodium sulfate can provide a certain quantity of sulfate radicals for electrochemical reaction in the electrolyte to reduce the degree of supersaturation of lead sulfate crystals; silicon-oxygen bonds and hydrogen bonds in the organic silicon polymer can effectively reduce the softening speed of the active substance, inhibit the passivation of the active substance on the surface layer and prolong the service life of the battery.

Description

Can improve the colloidal electrolyte in lead-acid battery life-span

Technical field

The invention belongs to lead-acid battery field, be specifically related to improve the colloidal electrolyte in lead-acid battery life-span.

background technology

Lead acid accumulator, since invention in 1859, because it has that raw material is extensive, cheap, the advantage such as dependable performance, Applicable temperature scope be wide, has been applied to multiple fields such as electric power, traffic, communication, automobile, railway.Through the technological innovation of more than 100 years, improve constantly energy content of battery density, cycle life and large current discharging capability etc., still there is the maximum market share in field of chemical power source at present.Lead-acid battery is mainly constructed by parts such as positive pole, negative pole, electrolyte, barrier film, housing, safety valve, terminals and is formed, and in valve-control type lead-acid accumulator, part electrolyte is absorbed in positive/negative plate and AGM dividing plate, makes battery be achieved sealing.

But lead-acid battery is in use found, there will be early stage capacitance loss, and it is known that the lead-acid battery that market is return carries out dissection and analysis failure cause, what accounting example was maximum is that positive plate active material softening and shedding causes battery capacity to decline, end-of-life.But, carrying out with circulating battery, positive material（PAM）softening is inevitably, because in battery charging and discharging, active material constantly transforms and causes anodal volumetric expansion to be shunk, adhesion declines.For delaying it, battery is had a negative impact, mostly most enterprises and research institution are to seek different additive to slow down active material softening, as conductive agent, fiber-like additive, organic additive etc., improve positive active material intensity, extending battery life, but effect is not remarkable.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of colloidal electrolyte that can improve the lead-acid battery life-span, can effectively reduce positive plate active material softening rate, thereby extends the life-span of lead-acid battery.

Technical solution of the present invention is as follows:

Can improve the colloidal electrolyte in lead-acid battery life-span, raw material by following mass percent forms, and polyethylene glycol 0.1 ~ 0.5%, stannous sulfate 0.1 ~ 1%, sodium sulphate 0.5 ~ 1.5%, phosphoric acid 0.5 ~ 1%, organosilicon polymer 0.05 ~ 2%, aerosil 0.5 ~ 8%, sulfuric acid 35 ~ 45%, all the other are deionized water.

Further preferred version is, molecular weight polyethylene glycol 4000 ~ 20000.

Further preferred version is that phosphoric acid solution concentration is 75%.

Further preferred version is that sulfuric acid solution concentration is 45%.

Further preferred version is that organosilicon polymer is one or more in organosiloxane, hydroxy silicon oil, containing hydrogen silicone oil, dimethicone.

Adopt after technique scheme, the invention has the beneficial effects as follows:

1, polyethylene glycol, as deflocculant, can prevent that colloid from before perfusion battery, gel or reunion occurring, and strengthens colloidal stability, forms stable three-dimensional net structure.

2, stannous sulfate can be oxidized to tetravalent tin, the ability that recharges after conductivity and the battery over-discharge of raising active material.

3, sodium sulphate can be electrochemical reaction a certain amount of sulfate radical is provided in electrolyte, reduces the degree of supersaturation of lead sulfate crystallization, prevents from generating the sulfuric acid lead layer of fine and close poorly conductive.

4, the particle diameter that phosphoric acid can refinement lead sulfate crystal grain.

5, the silicon oxygen bond in organosilicon polymer and hydrogen bond can effectively reduce active material softening rate, suppress top layer active material passivation, improve battery.

Embodiment

embodiment 1

In the present embodiment, molecular weight polyethylene glycol is 6000 to taking polyethylene glycol 0.2%(), stannous sulfate 0.8%, sodium sulphate 0.8%, solution concentration be 75% phosphoric acid 0.5%, organosilicon polymer 0.5% (organosiloxane, hydroxy silicon oil 1:1 mixture), aerosil 8%, the solution concentration sulfuric acid 35% that is 45%, all the other are deionized water.

The preparation method of the described colloidal electrolyte that can improve the lead-acid battery life-span, comprises the following steps: after aerosil, deionized water are mixed, and mix 30min with 4800r/min speed shear agitation, obtain colloid mother liquor A;

After stannous sulfate, sodium sulphate, phosphoric acid, organosilicon polymer is water-soluble with deionization respectively, mix and obtain mixed liquid B;

Again mother liquor A, mixed liquid B, sulfuric acid solution are mixed, stir 20min with the speed of 3000r/min, obtain colloidal electrolyte.

embodiment 2

In the present embodiment, molecular weight polyethylene glycol is 4000 to taking polyethylene glycol 0.5%(), stannous sulfate 0.5%, sodium sulphate 0.5%, phosphoric acid 0.8%, organosilicon polymer 1.0%(organosiloxane), aerosil 6%, sulfuric acid 38%, all the other are deionized water.All the other are implemented as embodiment 1.

embodiment 3

In the present embodiment, molecular weight polyethylene glycol is 20000 to taking polyethylene glycol 0.1%(), stannous sulfate 0.2%, sodium sulphate 1.5%, phosphatase 11 %, organosilicon polymer (hydrogen silicone oil, dimethicone 2:1 mixture) 0.15%, aerosil 4.5%, sulfuric acid 38%, all the other are deionized water.All the other are implemented as embodiment 1.

embodiment 4

In the present embodiment, molecular weight polyethylene glycol is 20000 to taking polyethylene glycol 0.1%(), stannous sulfate 0.2%, sodium sulphate 1.5%, phosphatase 11 %, aerosil 4.5%, sulfuric acid 38%, all the other are deionized water.All the other are implemented as embodiment 1.

To embodiment 1,2,3, embodiment 4 is as blank contrast test comparison.Above different electrolytes is added in 6-DZM-12 battery, carry out initial performance test according to GB, test data is in table 1.

The different embodiment battery testing of table 1 data

Test event	Embodiment 1	Embodiment 2	Embodiment 3	Comparative example 4
					Initial capacity/Ah	12.8	12.7	13.0	12.9
Charging acceptance/A	2.462	2.135	2.324	1.962
					-15 ° of low temperature/Ah	10.4	10.7	10.8	10.4
21.6A heavy-current discharge/min	27	28	28	27
					100%DoD cycle life/time	458	482	435	352

As can be seen from the table, be added with organosilicon polymer in electrolyte, little on battery initial capacity and cryogenic property impact, accept and cycle life but can significantly improve battery charging, under 100%DoD, battery cycle life can improve approximately 25%.

Claims

1. can improve the colloidal electrolyte in lead-acid battery life-span, it is characterized in that: the raw material by following mass percent forms, polyethylene glycol 0.1 ~ 0.5%, stannous sulfate 0.1 ~ 1%, sodium sulphate 0.5 ~ 1.5%, phosphoric acid 0.5 ~ 1%, organosilicon polymer 0.05 ~ 2%, aerosil 0.5 ~ 8%, sulfuric acid 35 ~ 45%, all the other are deionized water.

2. the colloidal electrolyte that can improve the lead-acid battery life-span as claimed in claim 1, is characterized in that: organosilicon polymer is one or more in organosiloxane, hydroxy silicon oil, containing hydrogen silicone oil, dimethicone.

3. the colloidal electrolyte that can improve the lead-acid battery life-span as claimed in claim 1, is characterized in that: molecular weight polyethylene glycol 4000 ~ 20000.

4. the colloidal electrolyte that can improve the lead-acid battery life-span as claimed in claim 1, is characterized in that: phosphoric acid solution concentration is 75%.

5. the colloidal electrolyte that can improve the lead-acid battery life-span as claimed in claim 1, is characterized in that: sulfuric acid solution concentration is 45%.