CN107546424A - A kind of combined additive of lead storage battery electrolytic solution and preparation method thereof - Google Patents
A kind of combined additive of lead storage battery electrolytic solution and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of combined additive of lead storage battery electrolytic solution and preparation method thereof, described combined additive is combined by 100 parts by volume silicone compositions and 3~30 parts by volume aerosils；Described silicone composition, which is based on 100 parts by volume, to be included：Main chain backbone is the parts by volume of siloxanes 1~10 of (Si O Si) structure and side base containing more than one unsaturated hydrophilic active groups；The parts by volume of organic silicon rubber 1~10；The parts by volume of industrial pure water 76.5~97.65；The parts by volume of lauryl sodium sulfate 0.3~3；The parts by volume of emulsifying agent 0.05~0.5；Described combined additive is prepared by process of the present invention, its mix sulphur acid solution is added inside lead accumulator, the anti-softening ability of positive electode of lead battery active material can be strengthened, there is the effect of helping softening active material to recover hardening, there is few, the cost-effective advantage of addition.
Description
Technical field
The present invention relates to the field of material technology of lead accumulator, more particularly to a kind of combination of lead storage battery electrolytic solution adds
Add material, formula of agent and preparation method thereof.
Background technology
In recent years, with photovoltaic generation industry, the development of wind power industry, the battery of market common requirements Large Copacity
Make energy storage with applying mechanically, but conventional battery shows short life in use out of doors, it is higher to discard rate, constrains photovoltaic energy storage system
The business application of system.Industry is generally accepted, and is added appropriate colloidal substance in the sulfuric acid liquid of lead accumulator, can effectively be lifted
The life-span used out of doors.
The colloidal materials that lead accumulator industry tradition uses are aerosil, during use by industrial pure water or other
Solvent method fully liquefies aerosil；In Chinese invention patent ZL01109623.3, disclose a kind of by poly- member
The silicone composition of plain siloxanes, organic silicon rubber and thinned water mixing, said composition store with the mixed poly- lead that is used as of sulfuric acid liquid
The electrolyte or forming liquid of battery.Applied by ten several years, industry generally believes aerosil colloid and silicone combinations
Thing colloid is each has something to recommend him, and the former viscosity is high, the income of manufacturability difference and lead accumulator without reduction internal resistance, increase capacity, but the life-span
Decay is more steady, and the latter's viscosity is low, good manufacturability and lead accumulator can obtain the income for reducing internal resistance, increasing capacity, but stably
Property is not so good as the former.
In recent years since, lead accumulator industry is seeking to one kind can be by aerosil colloid and silicone composition glue
The technical scheme that body has complementary advantages, but some methods and unsuccessful for simply mixing both, technical reason is：Conventional gas phase
Silicon dioxide colloid is a kind of aqueous-phase material, but described silicone composition is a kind of hydrophily oil phase thing, and both are simply mixed
The fine dispersion system closed and formed is unstable, and it is unsatisfactory to be added into the performance of the lead accumulator electrochemistry after electrolyte.Therefore,
Industry wishes to seek to one kind to be fully coupled aerosil and organic polymer composition, be added into can after sulfuric acid liquid
The combination colloidal additive of lead accumulator chemical property is lifted, lead accumulator is effectively extended outdoor service life, is dropped
The discarded rate of low battery.
The content of the invention
It is an object of the invention to：For aerosil colloid and siloxanes group in current lead accumulator industry market
The technological deficiency of compound colloid, there is provided a kind of that aerosil and silicone composition are fully coupled, are added into sulfuric acid liquid
The colloidal additive of lead accumulator chemical property can be lifted by making electrolyte, lead accumulator is effectively extended discharge and recharge and used the longevity
Life, reaching reduces technology application target of the battery using discarded rate.
To achieve the above object, the invention provides a kind of combined additive of lead storage battery electrolytic solution, described group
Additive is closed to be combined by 100 parts by volume silicone compositions and 3~30 parts by volume aerosils；Described siloxanes
Composition is based on 100 parts by volume, including following components and content：
Component A：Main chain backbone is (- Si-O-Si-) structure and side base contains more than one unsaturated hydrophilic active group R, divided
Siloxanes of the son amount less than 3000,1~10 parts by volume；
B component：Viscosity is less than the organic silicon rubber of 1500 pas, 1~10 parts by volume；
Industrial pure water：76.5~97.65 parts by volume；
Lauryl sodium sulfate：0.3~3 parts by volume, described lauryl sodium sulfate are to impregnate montmorillonite with sulfuric acid liquid
Saturated solution；
The parts by volume of emulsifying agent 0.05~0.5, described emulsifying agent include the one or more of following material：TWEEN Series breast
Agent, Span series emulsifying agent, triethanolamine, sodium carboxymethylcellulose, polyvinyl alcohol.
In the content of above-mentioned aerosil, described parts by volume is the scaled value of its weight/proportion；
In the component of combinations thereof additive, the R contained by the component A siloxanes side base includes H, OH, SO2H、NH2、CH3
Or other unsaturated hydrophilic active groups.
In the component of combinations thereof additive, the organic silicon rubber of the B component includes methyl silicone rubber, ethyl silicon rubber
Glue, methyl phenyl silicone rubber, the organic silicon rubber containing nitrile silicone rubber or containing other organic groups.
Based on above-mentioned material and ratio range, the stock is fabricated to the lead electric power storage present invention also offers one kind
The preparation method of the combined additive of pond electrolyte, this method include：
1) described component A and described B component are thoroughly mixed uniformly；
2) HLB of described emulsifying agent is adjusted to 7~9, then adds described industrial pure water, added after well mixed
In the mixture obtained to step 1), it is uniformly mixed；
3) mixture obtained to step 2) adds described lauryl sodium sulfate, is uniformly mixed；
4) described aerosil is added to mixture obtained by step 3), is well mixed, produces in being sufficiently stirred
To combined additive of the present invention.
In the preparation method of combinations thereof additive, described step 4) also includes：As set-up procedure 3) obtained by mixing
The material ratio of thing and aerosil adjusts the clarity of this step mixture.
Present invention also offers a kind of electrolyte of combined additive containing above-mentioned lead storage battery electrolytic solution or reparation
Liquid.The sulfuric acid liquid of the electrolyte or reparation liquid using density as 1.05-1.35 is key component, and the combined additive is described
The volume content of electrolyte is not less than 0.2%, is not less than 2% in the volume content of the reparation liquid.
In the present invention, the viscosity of the combined additive made of the material prescription and preparation technology is low, is added into sulfuric acid
Gel is slow after liquid, is typically added into the sulfuric acid liquid a few hours and still meets technological requirement to lead accumulator routine liquid filling, and
Versatility is good, can be used in mixed way with other conventional additives of lead storage battery electrolytic solution.
Before have described, aerosil colloid and silicone composition colloid have respective advantage and disadvantage, industrial gas
The spatial volume of aerosil belongs to non-type structure, and when its average grain diameter is more than tens nanometer, produced is inorganic
Colloid viscosity is big, gel is overrun, filling process is poor, and it is low that the lead accumulator of supporting making shows as initial capacity；And foregoing silicon
If silicone compositions can not be fabricated to the ball shape structure that particle diameter is less than 10 nanometers, the organic colloid that sulfuric acid liquid is produced is added into
Although viscosity is small, gel is slow, filling process is good, the chemical property of supporting making lead accumulator is equally undesirable, such as
Lead accumulator latter stage capacity attenuation speed is relatively large.
The combined additive of the present invention can preferably overcome conventional gas-phase silicon dioxide colloid and silicone composition colloid
The shortcomings that, by above-mentioned material prescription and preparation method, it is abundant with silicone composition that inorganic aerosil can be obtained
The combined additive of coupling, the combined additive, which adds sulfuric acid liquid, to be had to the preferable percdation ability of positive electode of lead battery,
Positive electode of lead battery active material lattice avalanche speed caused by lead sulfate oxidationreduction can be slowed down, positive-plate life is given
(the major technique reason of lead accumulator end-of-life is caused by positive material(PAM) softening, accounts for end-of-life probability for extension
80%), now described combined additive can be considered a kind of for extending the life-span reinforcing agent that uses of positive pole；Work as lead accumulator
When causing capacity attenuation because of positive material(PAM) softening, by adding a certain proportion of combined additive inside lead accumulator,
It is pressurized make it internally plate group be evenly distributed after, positive active material can be made by secondary formation charging technique known to industry
Again harden, recover positive electrode capacity, now described combined additive can be considered a kind of reparation for positive electrode capacity reparation
Solution additive.
A kind of combined additive of lead storage battery electrolytic solution of the present invention and preparation method thereof advantage is：
With the material prescription and preparation method of combined additive of the present invention, can produce a kind of has work(to lead accumulator
The combined additive of effect, the combined additive are added into sulfuric acid liquid and make electrolyte by a certain percentage, can effectively lift lead accumulator
Chemical property, and can be used as a kind of positive electrode capacity repair additive of lead accumulator, while can be with other hydrophilic lead
Battery additive is used in mixed way, and purposes is wide, and using effect is good.
Embodiment
With reference to embodiment further to a kind of combined additive of lead storage battery electrolytic solution of the present invention
Material, formula and its and its prepare process be described in detail.
Component A siloxanes of the present invention is one kind in macromolecule silicon compound, and its architectural feature is main chain backbone
Contain more than one unsaturation with m (- Si-O-Si-) segments, the positive integer of described m Wei≤1, its side base (side chain)
Hydrophilic active group R, wherein described R includes but is not limited to H, OH, SO2H、NH2、CH3Deng or other unsaturated parents
Water active group；In numerous main chain backbones in the siloxanes of (- Si-O-Si-) segmented structure, all side bases (side chain) contain insatiable hunger
It can select to be coupled with B component organic silicon rubber with the poly- element siloxanes of hydrophilic active group, to ensure component A and B groups
Divide and be easier to be coupled under normal conditions, and be easily diluted after being copolymerized with B component, the A groups that molecular weight should be selected to be less than 3000
Point.
A species in the organic silicon rubber category organosilicon material of the B component, its product line include methyl silicon rubber
Glue, ethyl silicon rubber, methyl phenyl silicone rubber, the organic silicon rubber containing nitrile silicone rubber or containing other organic groups, have different poly-
Right chain structure, with chain hop count n increases, molecular weight increases, and viscosity increases, and viscosity should be selected to be less than 1500 during application
The organic silicon rubber product of pa, such flowable organic silicon rubber are commonly called as liquid silastic；One of important function of B component,
It is the end-capping reagent of the molecular structure segment as component A, a kind of two-phase interface theory of electrochemistry thinks, (A+B) copolymerization is formed
Special compound bone add the set directed movement that sulfate liquid system is more beneficial for ion cluster, increase ion jumps in the channel
The ability moved, be advantageous to be formed the absorption electric double layer of dynamic equilibrium in electrode and electrolyte two-phase interface, strengthen ion in electrode
The activation energy of surface reaction, accelerates the speed of electrode reaction, so as to strengthen the high current respond of electrode.
Described industrial pure water is also known as industrial water, deionized water etc., because common source water salt content and pH value not
Together, these trace impurities can influence the production effect of the combined additive；Industrial pure water is routinely that source water is passed through into electrodialysis
Device method, ion-exchanger method, hyperfiltration and be made, industrial pure water of the present invention, the ion removed includes cation
And anion, technical requirements resistivity is more than 10 megohms.
Described lauryl sodium sulfate is also known as lauric alcohol (or laruyl alcohol) sodium sulphate, chemical formula C12H25SO4Na, it is one
Kind anion surfactant, it is soluble in water, it is good with anion, the multiple compatibility of nonionic, there is good dispersive property, industry
Product are white or flaxen micro- viscous thing, are usually used in detergent and textile industry.Lauryl sodium sulfate adds in present invention polymerization
It is dispersant as component A and B component copolymer to add in agent prescription, the active matter content in procurement of commodities it is general all compared with
Height, such as the active matter content of fluid product are general all >=27%；If use the powder product or pin of lauryl sodium sulfate
Shape product, because its active matter content is general all >=88%, it is directly used as the ineffective of dispersant, should be through industrial pure water during use
Or other solvents are diluted to use condition.
Described emulsifying agent is used for the hydrophilic lipophilic balance (HLB) in (A+B) copolymer described in preparation process regulation, root
The experience being about worth according to water-soluble method estimation HLB, the HLB of (A+B) copolymer being typically prepared are less than 9, directly use technical pure
The scattered effect of moisture is unsatisfactory, the HLB of emulsifying agent is adjusted to 7~9 and after being diluted with water to the scattered effect of (A+B) copolymer
Fruit is preferable.The range of choice of emulsifying agent is larger, and actual interpolation amount is for the purpose of by its HLB regulations to 7~9, described emulsifying agent
It is the common articles for use of pharmacy/chemical industry, such as tween (polyoxyethylene sorbitan fatty acid ester) is a kind of nonionic
Type surfactant, oil-in-water (O/W) type emulsifying agent and the solubilizer of oil phase substance are widely used as, with other emulsifying agents such as sapn
Class shares the stability that can increase emulsifying agent.The HLB of various emulsifying agents is each variant, even the emulsifying agent of same component,
Its HLB can be influenceed because of content, purity difference, recommend to compound regulation in described emulsifying agent, such as use TWEEN Series breast
Agent and sapn (sorbitan fatty acid ester) serial emulsifying agent carry out compounding regulation.
Described aerosil (white carbon) is that a kind of colloid known to lead accumulator manufacturing prepares material, its
Chemical formula is SiO2, the concentrated phosphoric acid of hydrofluoric acid and heat is soluble in, bases and can be melted and worked；Aerosil because of particle diameter very
Small, specific surface area is big, and superficial attractive forces are strong, and surface energy is big, and chemical purity is high, and dispersive property is good, has in thermal resistance, resistance etc.
There is specific performance, be always lead accumulator manufacturing colloidal electrolyte with its superior stability, reinforcing and thixotropy
Traditional material.Due to aerosil impalpable structure and in foam-like is accumulated, easily floated by moving air, true volume
Difficult accurate measuring, therefore aerosil parts by volume of the present invention, recommend to use volume instead and with proportion multiply in practical operation
Long-pending parts by weight metering.
The raw material of combination of the above additive can be purchased commercially, and the purity of the aerosil will
Ask and reach 99.99%, the purity requirement of the component A, B component and emulsifying agent is at least technical pure, and SILVER REAGENT more preferably, works as synthesis
During the contaminant overstandard of raw material, the synthetic effect of the combined additive is influenced whether, the combined additive of contaminant overstandard is added
Enter to the electrolyte for being added into lead accumulator, lead accumulator increase self discharge can be caused or even produce other side effects, meeting simultaneously
Influence the storage period of the combined additive.
The combined additive of lead storage battery electrolytic solution of the present invention can not use one kettle way to mix, and be followed after need to stocking up
Prepared by certain process, the preparation method includes：
1) described component A and described B component are thoroughly mixed uniformly；
2) HLB of described emulsifying agent is adjusted to 7~9, then adds described industrial pure water, added after well mixed
In the mixture obtained to step 1), it is uniformly mixed；
3) mixture obtained to step 2) adds described lauryl sodium sulfate, is uniformly mixed；
4) described aerosil is added to mixture obtained by step 3), is well mixed, produces in being sufficiently stirred
To combined additive of the present invention.
Above-mentioned steps 2) in, when the regulation that the emulsifying agent of one-component does not reach to the HLB of (A+B) copolymer requires,
The two or more compoundings of foregoing emulsifying agent can be used.In the optimization operation of step 4), in addition to as regulating step 3) obtained by
The material ratio of mixture and aerosil adjusts the clarity of mixture, when obtained mixture clarity deficiency
(generally with apparent viscosity big), can be as regulating step 3) obtained by the material ratio of mixture and aerosil adjust
The clarity of mixture, make the quality of obtained mixture more preferably.
In order that the quality of obtained combined additive is more preferable, the conventional filterer of increase can also be continued after step 4)
Skill.Described combined additive, if desired for long-term storage or as commodity selling, can continue to fit after step 4) is completed to prepare
Amount addition basic species such as sodium hydroxide adjusts its pH value to more than 10.
Being stirred in the preparation method can be carried out at normal temperatures and pressures, and described is stirred including rotatably stirring
Mix, the shearing stirring that periodicity or corner cut are random, can also heat, help reaction using compressive reaction kettle, such as in mixture
Be stirred during keep mixture temperature be 75 DEG C ± 15 DEG C；When adding reaction pressure to mix using reactor, kettle
Pressure is no more than 25MPa.
The combined additive of lead storage battery electrolytic solution of the present invention is a kind of typical micro- dispersoid, is made
Success associates larger with preparation method, and its production effect can be entered by Tyndall (Tyndall) phenomenon to colloidal dispersion
Performing check；It is known in industry, wavelength be 400-700mm light by microdispersed colloidal dispersion when, if dispersed glue
Body particle diameter, which is less than lambda1-wavelength, to be scattered, and current general experiment conclusion is：When the particle of colloidal dispersion system
During diameter≤94nm, luminous intensity is hit in scattering and the biquadratic of wavelength is inversely proportional.The Tyndall phenomenon of prepared combined additive
Substantially, illustrate that the making of this combined additive reaches Technology design target；Conversely, made combined additive body can be verified
It is unsuccessful.
More deep personnel, above-mentioned steps 1 are studied for this area) it can pass through completely to the preparation method described in step 4)
Regulation of the different component in mixed process carries out equivalent substitution；Such as when the mobility of mixture obtained by step 1) is good enough
When, step 2) and step 3) union operation though the preparation method of this kind of equivalent substitution is also operable, can easily be produced different
Structure body, it is possible to have influence on electrochemistry effect of final mixture.
In the specific implementation of the present invention, different selections and the married operation that feeds intake, as final mixture Stabilized
Under the premise of, it is possible that the contradiction of clarity and electrochemistry effect, the latter are often related to the aobvious state degree of Tyndall phenomenon.
When can'tting eat one's cake and have it, electrochemistry effect is recommended preferably to refine formula and technique.
The technical advantage of this combined additive is obvious, can be fabricated to a kind of pervasive additive agent electrolyte of lead accumulator, surely
It is periodically long, it is easy to store and transports, directly makes an addition to sulfuric acid liquid when using by a certain percentage as lead accumulator electrolyte, also may be used
It is used in mixed way with other conventional additives, when mixed with other additives, it is necessary first to when paying attention to mixed with other additives
Whether appearance precipitates or viscosity increases to and is difficult to be filled into inside lead accumulator, meanwhile, it is lifting lead as a kind of design object
The additive of accumulator property, it is necessary to completely examine to the performance of lead-acid battery for using other additives with, determined with cost performance
Fixed and other additives mixtures' ratios.
The electrolyte of lead accumulator sulfuric acid liquid, filling lead accumulator are prepared with combined additive of the present invention
With the obvious technical advantage of following items：
1st, the stable coupling of inorganic aerosil and silicone composition is realized, is reached aerosil glue
The technical advantage of body and silicone composition colloid is complementary, and the combined additive made is added into the sulfuric acid of lead accumulator
Liquid possesses the double technique advantage of aerosil colloid and silicone composition colloid；
2nd, after the combination colloidal additive is added to conventional sulfuric acid liquid, the life time decay of lead accumulator performance is more steady,
And lead accumulator can obtain increase capacity, reduce the income of internal resistance；
3rd, preferable anti-softening and capacity repairs effect to positive electode of lead battery active material.
4th, versatility is good：It can be used in mixed way with other conventional additives of lead accumulator；
5th, stability is good, adapts to storage, transports and sell the commodity turnaround time needed for each link.
Following examples are only used for further illustrating technical scheme, and these technical schemes can be used alone,
It can add or combine and use other mature technologies.
Embodiment 1
Design it is a kind of add lead accumulator sulfuric acid liquid, can increase the anti-softening ability of positive active material combination addition
Agent, the combined additive are mixed by 100 parts by volume silicon compositions and 3 parts by volume aerosils, wherein, silica
In terms of 100 parts by volume, component and content are alkane composition：
Component A：There is the siloxanes of some (- Si-O-Si-) segmented structures using a kind of main chain backbone, its side base contains H,
Molecular weight 1200, addition are 10 parts by volume；
B component：Viscosity be 1000 pas methyl silicone rubber, 10 parts by volume；
Industrial pure water：79.2 parts by volume；
Lauryl sodium sulfate：0.3 parts by volume；
The parts by volume of emulsifying agent 0.5：From span 20 and Tween 80, both, which are applied in combination, can make the stablizing effect of emulsification more
Good, wherein span 20 can adjust for 0.4 parts by volume, Tween 80 for 0.1 parts by volume, actual amount；
After completing stock, prepared using following process：
1) component A of 10 parts by volume and the B component of 10 parts by volume are thoroughly mixed uniformly；
2) described span 20 and Tween 80 are compounded, HLB is adjusted to 7, then add the technical pure of 79.2 parts by volume
Water, it is added in the mixture that step 1) obtains, is uniformly mixed after well mixed；
3) mixture obtained to step 2) adds the lauryl sodium sulfate of 0.3 parts by volume, is uniformly mixed；
4) by the mixture that step 3) obtains on the basis of 100 parts by volume, the aerosil of 3 parts by volume is added, is stirred
Mixing more than 15 minutes is mixed, that is, obtains described combined additive.
Above-mentioned preparation method is stirred at normal temperatures and pressures, and the combined additive of gained need to such as be deposited for a long time, then in right amount
The described sodium hydroxide of addition stock, the pH value of the combined additive is adjusted to 12.
The combined additive that the present embodiment obtains can be as a kind of wide spectrum additive of lead accumulator sulfuric acid liquid, according to not
Same purposes adds different proportion in the sulfuric acid liquid of lead accumulator.
Embodiment 2
Combined additive that embodiment 1 is obtained and lead accumulator sulfuric acid liquid that density is 1.245 by volume 1：99 is mixed
Closing, which uniformly, turns into a kind of silicone composition, silica and sulfuric acid liquid, mixes poly- colloidal electrolyte.
The present embodiment electrolyte is filled into inside lead accumulator of the 2V500Ah energy storage with valve-regulated AGM diaphragm structures, passed through
After conventional dipping, formation charging, turning into one has the extraordinary colloid plumbic storage battery of resistant to elevated temperatures outdoor energy storage.The present embodiment
Combined additive is with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions uses, and under the liquid-tight degree same case of sulfuric acid, can make
The effect that lead accumulator substantially obtains and reduces internal resistance, increases capacity.
In the present embodiment, the conventional anhydrous sodium sulfate of lead accumulator industry can be also added in described colloidal electrolyte,
Anhydrous sodium sulfate accounts for the 0.35% of the extraordinary colloidal electrolyte volume total amount, and industry is generally accepted, and is added in colloidal electrolyte
The anhydrous sodium sulfate of certain content, electrolyte electrochemical activity can be lifted, reduces the internal resistance of colloid plumbic storage battery, lifts colloid
The charge acceptance of lead accumulator.
Embodiment 3
In embodiment 1, silicone composition and the volume proportion of aerosil that the step 3) is prepared are
100：3, combined additive total amount is 103 parts by volume；The volume proportion is changed into 100 by the present embodiment：12, i.e. combined additive
Total amount change into 112 parts by volume, preparation method is same as Example 1.
Typically contrast effect test result on probation is：Silicone composition is different from the proportioning of aerosil, group
Different electrochemical properties can be shown by closing additive, and when combined additive is using silicone composition to be main, lead accumulator can
The income for obtain and reduce internal resistance, increasing capacity；And when increasing the mixed proportion of aerosil, what lead accumulator was shown
Cycle charge-discharge life time decay is more steady.
The combined additive of the present embodiment is with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions uses, and can make lead electric power storage
The cycle charge discharge electric life in pond is better than the effect of embodiment 2.
Embodiment 4
Design another electrolyte combination additive for adapting to the lead accumulator that long-term floating charge system uses, the combined additive
Mixed by the silicon composition of 100 parts by volume and the aerosil of 30 parts by volume, wherein, silicone composition with
100 parts by volume meters, component and content are：
Component A：Used siloxanes is that main chain backbone has some (- Si-O-Si-) segmented structures, and molecular weight is
1500, its side base contains SO2H, the parts by volume of addition 1；
B component：Viscosity be 1100 pas ethyl silicon rubber, 1 parts by volume；
Industrial pure water：95.95 parts by volume；
Lauryl sodium sulfate：2 parts by volume；
The parts by volume of emulsifying agent 0.05：It is standby for 0.04 parts by volume, Tween 80 from span 40 and Tween 80, wherein span 40
0.01 parts by volume, actual amount can adjust.
After completing stock, prepared using following process：
1) component A of 1 parts by volume and the B component of 1 parts by volume are thoroughly mixed uniformly；
2) described span 20 and Tween 80 are compounded, HLB is adjusted to 9, then add the technical pure of 95.95 parts by volume
Water, it is added in the mixture that step 1) obtains and is uniformly mixed after well mixed；
3) mixture obtained to step 2) adds the lauryl sodium sulfate of 2 parts by volume, is uniformly mixed；
4) mixture obtained to step 3) adds the aerosil of 30 parts by volume, and reaction is used in mixed process
Kettle, which pressurizes and heated, helps reaction, and kettle pressure is 20MPa, and it is 75 DEG C ± 10 DEG C that mixed process, which keeps the mixture temperature in kettle, is continued
It is stirred 30 minutes, then final gained mixture is filtered, it is described combined additive to take filtrate.In this step, such as
Fruit mixture clarity deficiency or viscosity it is bigger than normal, as micro set-up procedure 3) obtained by the material of mixture and aerosil
Ratio adjusts the clarity of this step mixture.
Content of the present embodiment because of aerosil in combined additive formula is higher, is made with suitable after sulfuric acid liquid
Large Copacity lead accumulator, it is especially suitable for the outdoor Large Copacity energy storage lead accumulator for making long-term floating charge state.
Embodiment 5
The combined additive that embodiment 1 is obtained uses the homogenizing processing of high-speed emulsifying machine, described high-speed emulsifying machine
Homogenizing rotary speed be more than 20000 revs/min, after the combined additive homogenized deep processing processing, with the lead that density is 1.20
Electrolyte acid liquid by volume 1：9 mixing are uniformly dispersed, and turn into a kind of and repair the special of positive electode of lead battery active material
With additive, market is commonly called as repairing liquid or renovation agent.
The reparation liquid of the present embodiment is added into through being judged as positive material(PAM) softening and held by quantifying for 1ml/10Ah
Inside the lead accumulator for measuring decay, the inner panel group point through adding negative pressure technique to make the reparation liquid in lead accumulator known to industry
After cloth is uniform, by secondary formation charging technique known to industry, the positive plate active material of softening is hardened again, treat this
The positive plate active material of the lead accumulator of reparation recovers capacity again.
It should be noted last that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although ginseng
The present invention is described in detail according to embodiment, it will be understood by those within the art that, to the technical side of the present invention
Case is modified or equivalent substitution, and without departure from the spirit and scope of technical solution of the present invention, it all should cover in the present invention
Right among.
Claims (6)
1. a kind of combined additive of lead storage battery electrolytic solution, it is characterised in that described combined additive is by 100 parts by volume
Silicone composition and 3~30 parts by volume aerosils combine；Described silicone composition is based on 100 volumes
Part, including following components and content：
Component A：Main chain backbone is (- Si-O-Si-) structure and side base contains more than one unsaturated hydrophilic active group R, molecular weight
Siloxanes less than 3000,1~10 parts by volume；
B component：Viscosity is less than the organic silicon rubber of 1500 pas, 1~10 parts by volume；
Industrial pure water：76.5~97.65 parts by volume；
The parts by volume of lauryl sodium sulfate 0.3~3, described lauryl sodium sulfate are the liquid that active matter content is not less than 27%
Body product；
The parts by volume of emulsifying agent 0.05~0.5, described emulsifying agent include the one or more of following material：TWEEN Series emulsify
Agent, Span series emulsifying agent, triethanolamine, sodium carboxymethylcellulose, polyvinyl alcohol.
2. the combined additive of lead storage battery electrolytic solution according to claim 1, it is characterised in that the component A silica
R contained by alkane side base includes H, OH, SO2H、NH2、CH3Or other unsaturated hydrophilic active groups.
3. the combined additive of lead storage battery electrolytic solution according to claim 1, it is characterised in that the B component has
Machine silicon rubber include methyl silicone rubber, ethyl silicon rubber, methyl phenyl silicone rubber, containing nitrile silicone rubber or containing other organic groups
Organic silicon rubber.
4. a kind of preparation method of the combined additive based on any lead storage battery electrolytic solution of claims 1 to 3, bag
Include：
1) described component A and described B component are uniformly mixed；
2) HLB of described emulsifying agent is adjusted to 7~9, then adds described industrial pure water, step is added to after well mixed
In the rapid mixture 1) obtained, it is uniformly mixed；
3) mixture obtained to step 2) adds described lauryl sodium sulfate, is uniformly mixed；
4) described aerosil is added to mixture obtained by step 3), is well mixed in being sufficiently stirred, that is, obtain this
The described combined additive of invention.
5. according to the method for claim 4, it is characterised in that described step 4) also includes：By set-up procedure 3) institute
The material ratio of mixture and aerosil adjusts the clarity of this step mixture.
6. the lead storage battery electrolytic solution containing any combined additive of claims 1 to 3 repairs liquid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111668557A (en) * | 2020-04-29 | 2020-09-15 | 广东英业达电子有限公司 | Colloid electrolyte of nano colloid long-life battery and preparation method thereof |
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| CN1374347A (en) * | 2001-03-13 | 2002-10-16 | 刘粤荣 | Organic polymer composition for lead accumulator and its prepn and use |
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| CN104617337A (en) * | 2015-02-21 | 2015-05-13 | 刘平 | Preparation method of lead-acid storage battery electrolyte |
| JP2015179588A (en) * | 2014-03-19 | 2015-10-08 | 三洋化成工業株式会社 | Additive agent for batteries |
| JP2016129117A (en) * | 2015-01-09 | 2016-07-14 | 日立化成株式会社 | Lead storage battery |
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| CN1374347A (en) * | 2001-03-13 | 2002-10-16 | 刘粤荣 | Organic polymer composition for lead accumulator and its prepn and use |
| JP2015179588A (en) * | 2014-03-19 | 2015-10-08 | 三洋化成工業株式会社 | Additive agent for batteries |
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| CN104617337A (en) * | 2015-02-21 | 2015-05-13 | 刘平 | Preparation method of lead-acid storage battery electrolyte |
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| CN111668557B (en) * | 2020-04-29 | 2022-03-18 | 广东英业达电子有限公司 | Colloid electrolyte of nano colloid long-life battery |
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