CN1157442C - Organic polymer composition for lead accumulator and its prepn and use - Google Patents
Organic polymer composition for lead accumulator and its prepn and use Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 64
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- 238000003860 storage Methods 0.000 claims description 44
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- 238000002360 preparation method Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- -1 vinylsiloxane Chemical class 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- XLXGCFTYXICXJF-UHFFFAOYSA-N ethylsilicon Chemical compound CC[Si] XLXGCFTYXICXJF-UHFFFAOYSA-N 0.000 claims description 3
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 25
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000001117 sulphuric acid Substances 0.000 abstract description 11
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 11
- 238000007599 discharging Methods 0.000 abstract description 4
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- 150000001875 compounds Chemical class 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 229910014559 C-Si-O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 235000019353 potassium silicate Nutrition 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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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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Abstract
The present invention relates to an organic macromolecular composition for lead accumulators, and a preparing method and uses as an electrolyte or a forming liquid thereof. The composition comprises 0.5 to 2 parts by volume of poly-element organosiloxane A, 0.5 to 2 parts by volume of organic silicone rubber B, 10 to 50 parts by volume of sulphuric acid C whose density is from 1.40 to 1.60 and 10 to 50 parts by volume of purified water D. The preparing method of the composition comprises the steps of the sufficient stir and mixing of the A and the B, the addition of the D and the addition of the C. The composition can be used as the electrolyte for a lead accumulator instead of diluted sulphuric acid, and the composition can be further diluted to be used as a forming liquid for manufacturing lead accumulator pole plates. The present invention has the functions of effectively enhancing the low-temperature electricity discharging capability of accumulators, prolonging the service life of accumulators, enhancing the electric property of all items of accumulators and lowering the corrosiveness of electrolytes to pole plates.
Description
The present invention relates to a kind of as lead storage battery ionogen or change into the composition of liquid, particularly relate to organic polymer composition that a kind of lead storage battery uses and preparation method and as ionogen or change into the liquid purposes.
The electrochemical principle of store battery is that the electrode with two kinds of different metals is dipped in acidity or the alkaline electrolyte, produces electrochemical action between one of them electrode is with electrolytic solution, then just has current potential to exist between electrode.The current potential extent is decided on the metal of composition electrode and the character of electrolytic solution.In the lead storage battery of routine, usually adopt the distilled water diluting vitriol oil as ionogen, changing into pole plate generally adopts dilute sulphuric acid to change into liquid in the technology manufacturing, because the serious reasons of overflowing of acid mist when dilute sulphuric acid changes in the pole plate energising, cause large-area environmental pollution when making chloride plate, become one of source of pollution to the manufacturing environment maximum of lead storage battery.A series of shortcomings such as structural relation and corrosive nature owing to electrolyte sulfuric acid and pole plate exist lead storage battery large current charge thermal value big, and work-ing life is short.In use there are hard nut to cracks such as acid mist effusion, interface corrosion in tradition open type lead acid cell, also fails thoroughly to solve the interface etching problem even install the general maintenance-free battery of reduced pressure sealing valve additional, all brings great inconvenience for transportation and use.
Repeatedly great reform has appearred in lead acid cell in nearly decades, wherein industrial process there is great effect, it is the valve controlled type sealed lead accumulator that the shallow company of Japanese soup took the lead in realizing the seventies in 20th century, the structural reform of this shell drops to than low degree the acid mist effusion of lead acid cell, and this sealed lead storage battery has obtained widespread use in communication, illumination and part train starting, traction field at present.In present technological transformation thinking, generally can be summed up as two classes: the one, on plumbic acid principle basis, pole plate is subtracted pound, for example adopt the measure that L glass fiber, conductive plastics replacement lead base grid etc. reduce the pole plate weight of covering.Another kind of innovation thinking is to seek the sulfuric acid pendular ring to protect substitute, and back one direction more and more obtains the various countries expert and payes attention to.As document 1 " solid electrolyte " (Shi Meilun work, science tech publishing house, 1982), introduce in the book: " high-energy-density battery " is as electrolytical with the beta-alumina pottery.Also has sosoloid battery etc.
In the ionogen that lead storage battery is used, except that present most widely used dilute sulphuric acid, also there is portioned product to adopt a kind of people alleged colloidal electrolyte usually.In history, when existing experiment found that micelle in the colloidal sol contact with solid as far back as 1809, Gu liquid---meeting formation electrostatic double layer on the two-phase interface.To the mechanism of this particle surface charge source, have multiple explanation at present in theory, as ionization, ionic adsorption, lattice replace, multiple theory such as particle is charged in the non-aqueous media.In industrial process, than adopting liquid electrolyte commonly used such as sulfuric acid, potassium hydroxide, the development of colloidal electrolyte is comparatively slow always, more influential in history practical colloid battery appears at phase early 1950s, and purpose is to solve the military vehicle starting problem of Korea battlefield under severe cold environment at that time.Nineteen sixty-five patent disclosure, this very early time is used the store battery of water glass colloidal electrolyte, is pushed to the commercial market first by German sunlight company.Through development decades, the ripe colloid storage battery of grasping with silicate ionogen main chemical compositions of existing at present many countries, this class colloidal electrolyte formula is all on the books in the patent documentation of various countries.Its advantage is to exempt to use bright sulfur acid, has tentatively adapted to electrolytical environmental protection demand; Shortcoming is that the specific energy of product is little than lead acid cell, and internal resistance is bigger, and in use dehydration sclerosis easily causes product performance and life-span all undesirable.Use the colloidal electrolyte of organic high molecular polymer, in disclosed patent or the technical literature report is being arranged seldom at present.
The objective of the invention is to:
1. the colloidal electrolyte of the organic high molecular polymer that the corrodibility of the application of the invention is lower replaces electrolyte sulfuric acid, improves lead storage battery interface extent of corrosion.
2. in order to reduce the acid mist escaped quantity of chloride plate manufacturing processed effectively, reduce the pollution of this technical process to manufacturing environment.
3. in order to reduce the corrodibility of ionogen, improve the work-ing life and the specific energy of lead storage battery to the internal storage battery pole plate;
4. in order to overcome the existing lead acid cell easy dehydration hardened of ionogen shortcoming in use, improve the comprehensive electric property of lead storage battery effectively, thus the organic polymer composition and the Preparation method and use that provide a kind of store battery to use.
The object of the present invention is achieved like this: the organic polymer composition that a kind of lead storage battery provided by the invention is used, and its composition comprises:
The A component is: molecular weight less than 3000, possess hydrophilic property and chemically active polyorganoelementosiloxane, wherein addition is the 0.5-2 parts by volume;
The B component: organo-silicone rubber, wherein addition is the 0.5-2 parts by volume;
The C component: density is 1.40-1.60g/cm
3Sulfuric acid, wherein addition is the 10-50 parts by volume;
The D component: pure water, wherein addition is the 10-50 parts by volume.
Also be included in and add sodium lauryl sulphate or water miscible polyvinyl alcohol (PVA) emulsifying agent in the blended A+B component, the emulsifying agent addition is 0.1～0.5 parts by volume.
Wherein the A component comprises: main chain backbone has the polyorganoelementosiloxane of m Si-O-Si or C-Si-O segmented structure, and side group (side chain) contains one or more unsaturated hydrophilic active radicals R, as: R is H, OH, SO
2H, NH
2, CH
3Or the like, in existing various countries Chemicals, belonged to conventional products, as the molecular weight supplied on the market less than 3000 " the hydrogenous organo-siloxane of side group ", " organo-siloxane of side group amino-contained " or chloride, contain alkoxyl group, hydroxyl, contain vinyl, amino-contained, contain organo-siloxanes such as cyclosiloxane, its structural formula is:
Or
The m=positive integer;
When composition of the present invention is used as the lead storage battery ionogen, need select the wetting ability and the chemically reactive of its polymkeric substance to the side group functional group of A component.It is ionogen that lead storage battery the two poles of the earth become the interior carrier of stream reaction, and the main component of the structure of matter of this composition remains sulfuric acid and water.The interpolation of A component and B component mainly is to be compounded to form with sulfuric acid and water the two poles of the earth are become the stronger gelling system of stream reactive behavior, is wetting ability to the requirement as the component A of gelling bone therefore, otherwise is difficult to form the stable gelling system that melts with water.The chemically reactive of A component side group functional group is selected, and should be again can not too weak group a little less than slightly than sulfate ion activity in the gelling system of planar water.Otherwise its chemically reactive is stronger than sulfate ion, can destroy sulfate ion status as the ion motion leading role in gelling system; And its chemically reactive too a little less than, the active reduction of ionogen that can cause this composition gelling system again can not be satisfied the basic demand that lead storage battery the two poles of the earth become the stream reaction.To the molecular weight requirement of A component, both needed to consider the factor of technology making processes, more will consider that the A component mixes the factor that the back forms the bigger polymkeric substance of molecular weight with the B component, therefore should select its molecular weight less than 3000, make it the flowability that can keep good.
Wherein organo-silicone rubber B component comprises: methyl silicone rubber, ethyl silicon rubber, vinylsiloxane rubber, phenyl siloxane rubber or contain the organo-silicone rubber of other organic group, should select the organo-silicone rubber of viscosity during application less than 1500 handkerchiefs.One of B component vital role in compound prescription be with the copolymerization of A component as A component molecular structure segment end-capping reagent.In the two-phase mixed system that (A+B component) copolymerization forms, when the reasonable ratio of (A+B component) and C component and D component, can produce and form numerous elementide active centre, the ion motion activity that improves in the combined electrolysis plastome is had special booster action.Research thinks that (A+B component) even existence in combined electrolysis plastome can be formed with the passage that is beneficial to the ion orientation movement, makes ion transition therein.Simultaneously, this combined electrolysis plastome helps setting up at electrode and electrolytic solution two-phase interface the absorption electrostatic double layer of dynamic stability, strengthen the activation energy of ion, electrode reaction is speeded up, thereby strengthened the large current discharging capability of acid storage battery in the electrode surface reaction.
C component and D component are used conventional sulfuric acid and the pure water of battery industry.
The preparation method of the organic polymer composition that lead storage battery of the present invention is used is undertaken by following technology:
1, at first get material ready by following component: get the A component and be molecular weight less than 3000, possess hydrophilic property and chemically active polyorganoelementosiloxane 0.5-2 parts by volume;
The B component is an organo-silicone rubber 0.5-2 parts by volume;
The C component is that density is 1.40-1.60g/cm
3Sulfuric acid, the 10-50 parts by volume;
The D component is a 10-50 parts by volume pure water,
2, then A component and B component are fully mixed;
3, the mixture with the step 2 behind the thorough mixing adds the dilution of 10-50 parts by volume pure water evenly again;
4, be 1.40-1.60g/cm with adding density in the mixture of step 3 then
3Sulfuric acid, the 10-50 parts by volume, when using as ionogen, best mode is to be filled in the store battery in general tens of minutes after mixing.
For making the A+B mixed system better mixed, also comprise the sodium lauryl sulphate or water miscible polyvinyl alcohol (PVA) emulsifying agent that can in the mixture of step 3, add 0.1～0.5 part.
It should be noted that the concentration range of choice of C component: when C component during with (A+B) chemical combination, the chemical combination concentration of C component is a key issue, and the selected concentration range of the present invention is preferable.Experiment shows that low excessively as the concentration of C component, meeting can not form full and uniform dispersion system because of active deficiency makes compound prescription, produces the coarse particles polymer too early, causes the ion motion ability of composite electrolyte to reduce.If the excessive concentration of C component may make (A+B component) mixed system by strong oxidation again, cause polymkeric substance dehydration carbonization, the ionic activity and the work-ing life of reducing composite electrolyte to occur.
The ionogen that the organic polymer composition that a kind of lead storage battery of providing of invention is used can use as lead storage battery, or further add the change into liquid of pure water dilution as battery plate.In the lead storage battery manufacture craft of routine, the density that is used as the dilute sulphuric acid of finished product battery electrolyte is generally 1.26-1.32g/cm
3The density that changes into the dilute sulphuric acid (abbreviation changes into liquid) of technology as the aluminium battery plate is generally 1.05-1.15g/cm
3, wherein being used to change into thickness is 1.05-1.08g/cm at 3mm with the sulfuric acid density of bottom crown
3, being used to change into thickness is 1.10-1.15g/cm at 3mm with the sulfuric acid density of top crown
3This ionogen and the sulfuric acid density benchmark that changes in the liquid have formed the standard system, all can find in general industry workshop manual.This composition is as ionogen and change into the sulfuric acid density benchmark of liquid, with conventional dilute sulphuric acid as ionogen and to change into the sulfuric acid density benchmark of liquid identical, be made as the purposes of example explanation organic polymer composition of the present invention below with lead storage battery:
1, composition of the present invention uses as the ionogen of lead storage battery; By C component and the compound same magnitude density to the normal temperature electrolyte sulfuric acid of D component ratio, using method is identical with conventional bright sulfur acid electrolyte.For example that the sulfuric acid density in the present invention's prescription is compound to 1.26-1.32g/cm
3, be added into the ionogen of in cotton adsorption type lead storage battery, doing of finishing assembling and use.During actual the use, the composite electrolyte that mixing forms is increased viscosity in time, progressively changes colloidal state into, therefore, and in the store battery of should packing into as early as possible.
2, when the further thin up present composition, but remain on the interior water yield of described composition ratio range, be diluted to pole plate and change into the required sulfuric acid density of liquid, for example prescription is diluted to sulfuric acid density 1.05～1.08g/cm
3, just can be used as pole plate and change into liquid and replace pure vitriolic and use; Chemical synthesizing method can adopt conventional pole plate to change into system.Adopt the benefit that changes into liquid behind the composition redilution of the present invention as pole plate, at first be because the existence of (A+B component) mixed system in dilute sulphuric acid, form prevention sulfuric acid mist evaporable barrier at liquid-air interface layer, reduced the acid mist escaped quantity of pole plate formation process, helped environmental protection.Help when changing into simultaneously at the surperficial activated adsorption layer that forms of plate active material, the electrostatic double layer that forms dynamic stability after polar plate solidification and the charging of assembling filling liquid is all had obvious effect.
Superiority of the present invention is:
1. use organic polymer composition of the present invention and do ionogen, reduced effectively lead storage battery make, use and discarded process to the pollution of environment.
2. use organic polymer composition of the present invention and make the store battery of electrolyte fabrication and effectively adapt to 0.5-2C (A) large current charge, the normal charge time foreshortens to 1-2 hour.
3. using organic polymer composition of the present invention, to do the store battery heavy-current discharge characteristic of electrolyte fabrication good, and the general lead acid cell of high-multiplying power discharge volume ratio is big more than 30%.
4. using organic polymer composition of the present invention, to do the store battery self-discharge of electrolyte fabrication little, and the capacity rate of descent of depositing of exempting to charge generally can be made to average every month＜2%.
5. using organic polymer composition of the present invention, to do the store battery cold property of electrolyte fabrication good, and than the big 20-40% of general lead acid cell ,-50 ℃ of environment still can satisfy big electric current and spark-10 ℃ of environment loading capacities.
6. this battery long service life generally can be made to the 500-2000 circulation and be filled time (75% surpassing deep discharge).
7. this battery possesses outstanding electric restorability, when battery uses to low potential, only needs very short time can return to noble potential certainly, continues output than macro-energy.When intermittent discharge or the use of non-steady load, its discharge voltage profile is indentation in time, and this discharge characteristic utmost point is suitable as power cell and uses.Research is thought, this characteristic is relevant in the system effect of ionogen and polar board surface electrostatic double layer with (A+B component), even under the low voltage electric field environment, the ion transition passage that (A+B component) dispersion system forms helps the pole plate electrostatic double layer to recover original distribution rapidly, thereby has improved the utilization ratio of plate active material.
When prescription of the present invention changed into liquid as pole plate, changing into liquid than conventional dilute sulphuric acid as pole plate had the tangible advantage in two aspects.At first be because after the present composition adds pure water dilution several times, composition forms jelly grade than dispersion system, because the proportion of (A+B component) is littler than sulfuric acid, assemble to changing into liquid-air interface morely, formed and intercepted the interfacial layer that sulfuric acid is upwards overflowed, the sulfuric acid that most of attempt is overflowed will make the acid mist escaped quantity of technique for making polar plate process reduce one or two order of magnitude by the constraint of gel microbody system in interfacial layer, help the environmental protection of technique for making polar plate process.In addition, in dilute sulphuric acid, be (the A+B component) that form exists with a differential prose style free from parallelism, some energising activation of following pole plate to the plate active material surface seepage, is formed the adsorption layer of polar board surface.This adsorption layer had both been strengthened the state of cure of plate active material, also helps pole plate simultaneously and set up the electrostatic double layer that dynamic stability distributes in ionogen, and large current discharging capability and the low temperature discharge ability that improves store battery all had obvious effect.
The present invention is described in more detail below in conjunction with drawings and Examples:
Fig. 1 a-c be with composition of the present invention when the ionogen, a 12V.17Ah lead storage battery of made is respectively with " voltage-time " curve of shelving 1 hour after pressure limiting 17V10.2A charging, the charging and discharging with the 3.4A constant current
Fig. 2 is that a 12V.38Ah store battery of made is at-10 ℃ of low temperature environments " voltage-time " curve with the 10.89A discharge when being used as ionogen with composition of the present invention
Fig. 3 is when being used as ionogen with composition of the present invention, a 12V.38Ah store battery of made " voltage-time " curve of 30.4A (0.8C) constant current secondary intermittent discharge
Fig. 4 is when being used as ionogen with composition of the present invention, a 12V.38Ah store battery of made " voltage-time " curve of 6.6A constant-current discharge
Fig. 5 a-d is when using with the affected ionogen of composition of the present invention, and a 12V.17Ah store battery of made is used " voltage-time " curve and battery " energy-time " curve of 3.4A, 17A and 25A constant-current discharge respectively
Fig. 6 a-b is that a 12V.38Ah store battery of made is used " voltage-time " curve of 66A and 264A constant-current discharge respectively when being used as ionogen with composition of the present invention
Among Fig. 3---line is represented constant current 30.4A (0.8C) discharge curve;-----line is represented zero load;
Among Fig. 4---line is represented constant current 30.5A (0.8C) discharge curve;-----line is represented zero load.
Prepare the ionogen that a kind of lead storage battery uses, below describe the composition and the preparation method of the organic polymer composition that this lead storage battery uses in detail, the proportioning of the organic polymer composition that lead storage battery is used:
A. get molecular weight and be 1200 contain H polysiloxane, 1 parts by volume; With
B. the methyl silicone rubber of viscosity 850,1 parts by volume;
C. density is 1.58 sulfuric acid, 31.5 parts;
D. pure water is 29.5 parts, and above raw material all is to buy on the market.
And preparation as follows: 1, by said ratio with A component and component B fully mixed even after, again with D component dilution, be added into the C component at last and be mixed into composite electrolyte, be filled into one at once and finish that pole plate changes into and equipped every cotton adsorption type lead storage battery (12V17Ah).After irritating liquid, said composition promptly can be used as the lead storage battery ionogen and uses, end during with 3A electric current supplementary charging (also claiming that secondary changes into) during use to battery terminal voltage 15.6～16.0V, continue charging after the discharge again, it is respectively with shelving 1 hour after pressure limiting 17V10.2A charging, the charging and showing with 3.4A constant current discharge " voltage-time " curve such as Fig. 1 a-c.
Prepare the liquid that changes into that a kind of lead storage battery uses, below describe the composition and the preparation method of the organic polymer composition that this lead storage battery uses in detail, the proportioning of the organic polymer composition that lead storage battery is used:
A. molecular weight 1600 side groups contain CH
3With the polysiloxane of H, 2 parts by volume;
B. viscosity is less than 1000 ethyl silicon rubber, 1.8 parts by volume;
C. density is 1.40 sulfuric acid, 50 parts by volume;
D. surplus is a pure water, and above raw material all is to buy on the market.
Its preparation method is as follows: by above-mentioned proportioning weighing, earlier the A component is mixed with the B component fully and stir, after adding 30 parts of pure water dilutions then, mix with sulfuric acid again, be adjusted to till 1.07 until the sulfuric acid density with mixture by adding pure water at last, the liquid that changes into that made composition can be used as grid type plate uses; When as grid type plate change into liquid the time, step mode and conventional sulfuric acid liquid to change into step mode identical.In the pole plate formation process, the acid mist escaped quantity obviously lacks an order of magnitude when becoming with the bright sulfur acidifying, thereby has improved the air environmental protection index of this technology.After pole plate changed into and finishes, technology was finished assembling routinely, was filled into embodiment 1 described composite electrolyte, and the secondary chemical synthesizing method is identical.At a 12V.38Ah store battery that adopts this processing method to make, " voltage-time " curve during its low temperature discharge as shown in Figure 2.
In the conventional preferred embodiment of another kind, the combination matching of embodiment 1 can be adjusted, the proportioning of C component and D component is adjusted into 32 parts and 21 parts respectively, the proportioning of A component and B component is constant, and making processes is identical.Intermittent discharge " voltage-time " curve of a 12V.38Ah store battery of producing with present method as shown in Figure 3.
In another conventional embodiment, the 12V.38Ah store battery that the pole plate that adopts embodiment 2 methods to change into out is equipped with out.Electrolyte formula adds 0.5 part of sodium lauryl sulphate on the basis of embodiment 1 prescription, fully mixed in A component and B component mixed processes, all the other making methods are identical with embodiment 1." voltage-time " curve of using the discharge of 6.6A constant current of this store battery as shown in Figure 4.
In a kind of preferred embodiment of routine, adopt proportioning to make the ionogen that the present invention is used for store battery:
A. molecular weight 1600 contains NH
2Polysiloxane, 0.9 part;
B. viscosity is less than 1000 methyl silicone rubber, 1.1 parts;
C. density is 1.50 sulfuric acid, 32 parts;
D. diluting water is 24 parts.
Prescription blending means and using method are identical with embodiment 1.The lead storage battery of a 12V17Ah who produces with the can of this composition, it sees Fig. 5 a-d with " voltage-time " curve and " energy-time " curve of 3.4A, 17A and the discharge of 25A constant current respectively.
In another conventional preferred embodiment, adopt prescription:
A. molecular weight 1100 side groups contain the polysiloxane of H, 1 part;
B. viscosity is less than 1000 methyl silicone rubber, 1.1 parts;
C. density is 1.53 sulfuric acid, 28 parts;
D. diluting water is 26 parts.
Elder generation is mixed the A component during mixing with the B component, and elder generation adds 2 parts of water and 0.3 part of water miscible polyvinyl alcohol when mixed, and is mixed with D component and C component again after fully mixing, and all the other filling liquid chargingmethods are identical with embodiment 1.Battery plate changes into liquid on this prescription basis, and further being diluted to sulfuric acid density with pure water is 1.08, adopts conventional pole plate energising to change into system.With the 12V38Ah lead storage battery that present method is produced, " voltage-time " curve that it discharges with 66A and 264A constant current respectively, as shown in Figure 6.
Embodiment 7
On the basis of embodiment 1, also be included in the mixed middle sodium lauryl sulphate or water miscible polyvinyl alcohol (PVA) emulsifying agent of adding of A+B component, the emulsifying agent addition is that 0.1 or 0.5 parts by volume all can.Because add the faster formation of mixed system that emulsifying agent can make the A+B component, degree of mixing is better, other proportioning is identical with embodiment 1 with method for making.When doing ionogen with present method, though it is substantially the same manner as Example 1 aspect the electricity function index of can store battery, but the nature of the normal temperature after being mixed with ionogen gelation time is prolonged, and therefore compares with embodiment 1, and it is equipped that present embodiment more helps industry.
On the basis of embodiment 2, also be included in A+B component mixed and add sodium lauryl sulphate or water miscible polyvinyl alcohol (PVA) emulsifying agent, the emulsifying agent addition is 0.1 or all can to 0.5 parts by volume.Because owing to add the faster formation of mixed system that emulsifying agent can make the A+B component, degree of mixing is better, other proportioning is identical with embodiment 2 with method for making.Make when changing into liquid of present method, because little gelling system emulsification degree of (A+B component) is better, more help this little gelling system to the plate active material surface seepage when changing into, the degree that intercepts the acid mist effusion simultaneously in the chemical synthesis technology process is better than embodiment 2, is more conducive to environmental protection.
Embodiment 9
Only change the B component on the basis of embodiment 5, to adopt the B component be viscosity less than 1000 the phenyl siloxane rubber that contains, 2 parts by volume; All the other proportionings are constant, make the ionogen that the present invention is used for store battery:
Only change the A component on the basis of embodiment 5, the R that adopts A component side group to contain is CH
3And SO
2H, 2 parts of polysiloxane, all the other proportionings are constant, make the ionogen that the present invention is used for store battery.The component content of above embodiment all calculates with parts by volume, and density unit is g/cm
3
Claims (6)
1. organic polymer composition that lead storage battery is used comprises following component and content:
The A component. molecular weight is less than 3000 polyorganoelementosiloxane, and its structural formula is:
Side group R is selected from H, OH, SO
2H, NH
2Or CH
3, m is a positive integer,
0.5-2 parts by volume;
The B component. organo-silicone rubber 0.5-2, parts by volume;
The C component. density is 1.40-1.60g/cm
3Sulfuric acid, the 10-50 parts by volume;
The D component. dilution pure water, 10-50 parts by volume.
2. the organic polymer composition that a kind of lead storage battery as claimed in claim 1 is used is characterized in that: described B component is selected from methyl silicone rubber, ethyl silicon rubber, vinylsiloxane rubber or phenyl siloxane rubber, and its viscosity is less than 1500 handkerchiefs.
3. method for preparing the organic polymer composition that the described lead storage battery of claim 1 uses, it is characterized in that: order is carried out according to the following steps:
(1), at first gets the raw materials ready by following composition and content;
The A component is: molecular weight is less than 3000 polyorganoelementosiloxane, and its structural formula is:
Side group R comprises and is selected from H, OH, SO
2H, NH
2Or CH
3A kind of group, m is a positive integer,
Its addition is the 0.5-2 parts by volume;
The B component: organo-silicone rubber, its addition are the 0.5-2 parts by volume;
The C component: density is 1.40-1.60g/cm
3Sulfuric acid, the 10-50 parts by volume;
D component: pure water, 10-50 parts by volume;
(2), then with above-mentioned A component of getting ready and B component thorough mixing, stir;
(3), the dilution of tret D component 10-50 parts by volume is even again in the mixture that step (2) is obtained;
(4), C component 10-50 part will be added in the mixture of step (3).
4. the method for the organic polymer composition that preparation lead storage battery as claimed in claim 3 is used, it is characterized in that: add sodium lauryl sulphate or water miscible polyvinyl alcohol emulsifying agent in the mixture of step (3), the emulsifying agent addition is the 0.1-0.5 parts by volume.
5. the organic polymer composition that lead storage battery as claimed in claim 1 is used is characterized in that: when the organic polymer composition that described store battery uses changed into the liquid use as chloride plate, D component addition was the 50-300 parts by volume.
6. the purposes of the organic polymer composition used of claim 1 or 2 described lead storage batterys is characterized in that: the ionogen that described organic polymer composition uses as lead storage battery.
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| CNB011096233A CN1157442C (en) | 2001-03-13 | 2001-03-13 | Organic polymer composition for lead accumulator and its prepn and use |
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| CNB011096233A CN1157442C (en) | 2001-03-13 | 2001-03-13 | Organic polymer composition for lead accumulator and its prepn and use |
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| CN1157442C true CN1157442C (en) | 2004-07-14 |
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104538679B (en) * | 2015-01-14 | 2017-07-28 | 山东大学 | A kind of application of organo-silicon compound as additive in colloid storage battery |
| JP6699119B2 (en) * | 2015-01-22 | 2020-05-27 | 株式会社リコー | Element and power generator |
| CN107579286A (en) * | 2017-08-29 | 2018-01-12 | 东莞恒量新能源科技有限公司 | A kind of mixed poly- additive of lead accumulator and preparation method thereof |
| CN107579285A (en) * | 2017-08-29 | 2018-01-12 | 东莞恒量新能源科技有限公司 | A kind of combined additive of lead accumulator and preparation method thereof |
| CN107611490A (en) * | 2017-08-30 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of mixed poly- additive for lead accumulator and preparation method thereof |
| CN107611496A (en) * | 2017-08-30 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of combined additive for lead accumulator and preparation method thereof |
| CN107546424A (en) * | 2017-08-30 | 2018-01-05 | 东莞恒量新能源科技有限公司 | A kind of combined additive of lead storage battery electrolytic solution and preparation method thereof |
| CN107611489A (en) * | 2017-08-30 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of mixed poly- additive of lead storage battery electrolytic solution and preparation method thereof |
| CN107611492A (en) * | 2017-09-05 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of two-phase of lead accumulator mixes poly- additive and preparation method thereof |
| CN107611493A (en) * | 2017-09-05 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of two-phase combined additive of lead accumulator and preparation method thereof |
| CN107623146A (en) * | 2017-09-13 | 2018-01-23 | 东莞恒量新能源科技有限公司 | A kind of two-phase combined additive, purposes and preparation method thereof |
| CN107623145A (en) * | 2017-09-13 | 2018-01-23 | 东莞恒量新能源科技有限公司 | A kind of two-phase for lead accumulator mixes poly- additive and preparation method thereof |
| CN107579290A (en) * | 2017-09-18 | 2018-01-12 | 东莞恒量新能源科技有限公司 | A kind of two-phase compositions additive, purposes and preparation method thereof |
| CN107611494A (en) * | 2017-09-18 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of two-phase for lead accumulator mixes polymers additive and preparation method thereof |
| CN107565175A (en) * | 2017-09-18 | 2018-01-09 | 东莞恒量新能源科技有限公司 | A kind of two-phase compositions of lead accumulator and preparation method thereof |
| CN107634270A (en) * | 2017-09-18 | 2018-01-26 | 东莞恒量新能源科技有限公司 | A kind of two-phase for lead accumulator mixes polymers and preparation method thereof |
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