CN107565173A - A kind of two-phase polymeric additive of lead accumulator and preparation method thereof - Google Patents
A kind of two-phase polymeric additive of lead accumulator and preparation method thereof Download PDFInfo
- Publication number
- CN107565173A CN107565173A CN201710791653.XA CN201710791653A CN107565173A CN 107565173 A CN107565173 A CN 107565173A CN 201710791653 A CN201710791653 A CN 201710791653A CN 107565173 A CN107565173 A CN 107565173A
- Authority
- CN
- China
- Prior art keywords
- volume
- parts
- polymeric additive
- component
- lead accumulator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides two-phase polymeric additive of a kind of lead accumulator and preparation method thereof, described two-phase polymeric additive is based on 100 parts by volume, and component and content include：Main chain backbone is the parts by volume of siloxanes 1~7 of (Si O Si) structure and side base containing more than one unsaturated hydrophilic active groups；The parts by volume of organic silicone oil 1~7；10% 50wt% methyl silicate, 5~80 parts by volume；The parts by volume of industrial pure water 10~88；The parts by volume of aerosil 3~15；The parts by volume of emulsifying agent 0.1~0.5；Described two-phase polymeric additive is prepared by process of the present invention, it mixes conventional sulfuric acid liquid and added inside lead accumulator, the anti-softening ability of positive active material can be strengthened, help softening positive active material to harden again, 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, the two phase-polymerizations addition of more particularly to a kind of lead accumulator
The material of agent, formula and preparation method thereof.
Background technology
In recent years the battery of energy storage market common requirements Large Copacity is made with applying mechanically, but conventional battery table in use out of doors
Reveal short life, discarded rate is higher, constrains the business application of energy storage.Industry is generally accepted, in the sulfuric acid liquid of lead accumulator
Appropriate colloidal substance is added, can effectively lift the life-span.
The colloid that lead accumulator tradition uses is aerosil, passes through industrial pure water or other solvent methods during use
Aerosil is fully liquefied；In Chinese invention patent publication number CN1383225A, one kind is disclosed by poly- elemental silicon
The silicone composition of oxygen alkane, silicone oil and the mixing of positive silicic acid aqueous solution of ester, said composition polymerize with sulfuric acid liquid is used as lead accumulator
Electrolyte or forming liquid.Applied by ten several years, industry generally believes that aerosil colloid and high molecular weight siloxane gather
Rubber alloy body is each has something to recommend him, and the former viscosity is high but life time decay is more steady, the latter's viscosity is low and lead accumulator can obtain reduce internal resistance,
Increase the income of capacity, but stability is not so good as the former.
Lead accumulator industry is seeking to one kind can be mutual by aerosil colloid and silicone composition colloid advantage
The technical scheme of benefit, but some methods for being simply used in mixed way two class colloids and unsuccessful, technical reason is：Conventional gas phase two
Silicon oxide 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
Fine dispersion system it is unstable, and be added into the lead accumulator electrochemistry after electrolyte performance it is unsatisfactory.Therefore, industry is wished
Seek to one kind after being fully coupled aerosil and silicone composition, be added into sulfuric acid liquid that lead accumulator can be lifted
The aggregation colloid additive of chemical property.
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 two-phase polymeric additive of lead accumulator, described two-phase
Polymeric additive 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 3000,1~7 parts by volume；
B component：Viscosity is less than the organic silicone oil of 2000 pas, 1~7 parts by volume；
Component C：10%-50wt% methyl silicate, 5~80 parts by volume；
Industrial pure water：10~88 parts by volume；
Aerosil：3~15 parts by volume；
The parts by volume of emulsifying agent 0.1~0.5, 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 above-mentioned two-phase polymeric additive, the R contained by the component A siloxanes side base includes H, OH, SO2H、
NH2、CH3Or other unsaturated hydrophilic active groups.
In the component of above-mentioned two-phase polymeric additive, the B component organic silicone oil includes methyl-silicone oil, ethyl silicon oil, benzene
Base silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, cyanoethyl methyl polysiloxane or the organic silicone oil containing other organic groups.
In the component of above-mentioned two-phase polymeric additive, the alkalescence tune that preparation process is used to adjust mixture pH value is additionally included in
Whole dose.Described alkaline regulator includes sodium hydroxide or potassium hydroxide but is not limited to sodium hydroxide or potassium hydroxide.
Based on the material and ratio range of above-mentioned two-phase polymeric additive, present invention also offers one kind by the stock
The preparation method of the two-phase polymeric additive of the lead accumulator is fabricated to, this method includes：
1) described emulsifying agent is divided into two parts, it is standby；
2) described component A and described B component are thoroughly mixed and uniformly, then add described component C, fully
It is uniformly mixed；
3) described a copy of it emulsifying agent is used to adjust the HLB of mixture obtained by step 2) to 10~14；
4) HLB of another described emulsifying agent is adjusted to 10~14, adds described industrial pure water, be sufficiently mixed
It is even, described aerosil is then added, is thoroughly mixed uniformly；In this step, including by adjustment contain emulsifying agent
Industrial pure water and the ratio of aerosil adjust the clarity of final mixture；
5) mixture that step 3) obtains is well mixed with the mixture that step 4) obtains in being sufficiently stirred, that is, obtained
Two-phase polymeric additive of the present invention.In this step, it is included in blend step 3) before obtained mixture, with described
Alkaline regulator adjusts the pH value of mixture obtained by step 4) to 8-10.
Present invention also offers a kind of lead storage battery electrolytic solution containing above-mentioned two-phase polymeric additive or repair liquid.It is described
The sulfuric acid liquid of electrolyte or reparation liquid using density as 1.05-1.35 is key component, and the two-phase polymeric additive is in the electricity
The volume content for solving liquid 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 for the two-phase polymeric additive produced with the material prescription and preparation technology is low, addition
Gel is slow after entering sulfuric acid liquid, is typically added into sulfuric acid liquid a few hours and still meets technological requirement to lead accumulator routine liquid filling, and
And versatility is good, can be used in mixed way with other conventional additives of lead storage battery electrolytic solution.
Aerosil colloid and silicone composition colloid have respective advantage and disadvantage, the space of aerosil
Volume belongs to non-type structure, and when its average grain diameter is more than tens nanometer, produced inorganic colloid viscosity is big, filling work
Skill is poor, and it is low that the lead accumulator of supporting making shows as initial capacity；And if aforementioned silicone composition can not make granulating
Footpath is less than 10 nanometers of ball shape structure, although being added into, the organic colloid viscosity that sulfuric acid liquid is produced is small, filling process is good,
The latter stage capacity attenuation speed of supporting making lead accumulator is relatively large.
The shortcomings that two-phase polymeric additive of the present invention can overcome aerosil colloid and silicone composition colloid,
Inorganic aerosil is set to obtain fully coupling with silicone composition, the additive adds sulfuric acid liquid to chloride plate
With percdation ability, positive active material lattice avalanche speed caused by lead sulfate oxidationreduction can be slowed down, make circulation
Life-span must give extension, and (the main reason for lead accumulator end-of-life is caused by positive material(PAM) softening, accounts for end-of-life
Probability 80%), now two-phase polymeric additive of the present invention can be considered a kind of reinforcing agent used for positive pole.Similarly,
Capacity attenuation lead accumulator to confirming positive material(PAM) softening, additive of the present invention add sulfuric acid liquid and can be considered one
Kind lead accumulator repairs liquid.
A kind of two-phase polymeric additive of lead accumulator of the present invention and preparation method thereof advantage is：
With material prescription of the present invention and preparation method, can produce a kind of has the two of effect to lead accumulator
Phase-polymerization additive, the two-phase polymeric additive are added into sulfuric acid liquid and make electrolyte by a certain percentage, can effectively lift lead electric power storage
The chemical property in pond, and can be used as a kind of positive electrode capacity repair additive of lead accumulator, while can be hydrophilic with other
Lead accumulator additive, which mixes, to be used, and purposes is wide, and using effect is good.
Embodiment
With reference to embodiment further to a kind of material of the two-phase polymeric additive of lead accumulator 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 silicon-containing polymer, and its architectural feature is main chain bone
Frame has m (- Si-O-Si-) segments, the positive integer of described m Wei≤1, and its side base (side chain) contains more than one insatiable hunger
With hydrophilic active group R, wherein described R includes but is not limited to H, OH, SO2H、NH2、CH3Deng or other are unsaturated
Hydrophilic active group；In numerous main chain backbones in the siloxanes of (- Si-O-Si-) segmented structure, all side bases (side chain) are not containing
The poly- element siloxanes of saturation hydrophilic active group can select to be coupled with B component organic silicone oil, 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 silicone oil category organosilicon material of the B component, also known as silicone grease, silicon emulsion, silicon emulsifying agent
Include methyl-silicone oil, ethyl silicon oil Deng, described organic silicone oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, contain
Nitrile silicone oil or the organic silicone oil containing other organic groups, there is the chain structure of different polymerization degree, the molecule with chain hop count n increases
Amount increase, viscosity increases, and viscosity should be selected during application to be less than the organic silicone oil product of 2000 pas；One of important function of B component,
It is the end-capping reagent of the molecular structure segment as component A.
Described component C is the 10%-50wt% methyl silicate aqueous solution, and the chemical formula of methyl silicate is
C4H12O4Si, it is good organic solvent and organic synthesis intermediate, there is both sexes coupling, the important function of component C
One of, be it is both easily full cross-linked with hydrophilic component A, again can be full cross-linked with oil loving B component, therefore component C
When being copolymerized with component A and B component, the scattered silicone combinations objects system evenly of differential is easily formed；A kind of two-phase interface is theoretical
Think, the special compound bone of the copolymerization formation of (A+B+C), the segmented structure after (A+B+C) copolymerization can be made in electrolyte system
Middle formation is more beneficial for the passage that ion cluster gathering closes directed movement, the ability of increase ion set transition in the channel, meanwhile,
This combined electrolysis plastidome is advantageous to the absorption electric double layer of the two-phase interface formation dynamic equilibrium of middle electrode and electrolyte, strengthens
The activation energy that ion reacts in electrode surface, accelerate the reaction speed of electrode, 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 two-phase polymeric additive；Industrial pure water is routinely that source water is passed through into electricity
Dialyzer method, ion-exchanger method, hyperfiltration and be made, industrial pure water of the present invention, the ion removed include sun
Ion and anion, technical requirements resistivity is more than 10 megohms.
Described emulsifying agent is used to prepare the hydrophilic lipophilic balance of two-phase polymeric additive procedure regulation intermediate
(HLB).Such as the experiences that are about worth of HLB are estimated according to water-soluble method, the HLB of (A+B+C) copolymer being typically prepared 7~
9, when polymerizeing with aqueous-phase material, its HLB is adjusted to 10~14 adaptation value, polymerization effect can be more preferable；Rule of thumb, exist simultaneously
Industrial pure water addition is adjusted to HLB 11~14 emulsifying agent, and the effect for disperseing aerosil can be more preferable；The 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, is for example taken charge of with other emulsifying agents
Disk (sorbitan fatty acid ester) class emulsifying agent compounding can increase the stability of emulsification.The HLB of various emulsifying agents is each variant,
Even same component emulsifying agent also can influence its HLB because content, purity are different, according to requiring HLB when specifically used
It is different and it is preferred that compound regulation, such as with the required HLB of tween emulsifier type and the compounding regulation of spans emulsifying agent.
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.
Described alkaline regulator, effect be adjust mixture preparation process intermediate pH value, it include it is all can
Adjustment mixture pH value will not produce the alkaline regulator of sediment again, and alkaline regulator is in the two-phase polymeric additive
Belong to micro in content, select face wider, but consider preferred sodium hydroxide or potassium hydroxide from cost performance.Such as sodium hydroxide is one
Kind highly basic, is a kind of the most frequently used alkaline regulator of lead accumulator industry.
Above-described raw material can be purchased commercially, and the purity requirement of the aerosil reaches
99.99%, the purity requirement of the component A, B component, component C and emulsifying agent is at least technical pure, and SILVER REAGENT more preferably, works as former material
During the contaminant overstandard of material, the synthetic effect of the two-phase polymeric additive is influenced whether, two phase-polymerizations of contaminant overstandard are added
Agent is added into the electrolyte of lead accumulator, can cause lead accumulator increase self discharge or even produce other side effects, while can shadow
Ring the storage period of the two-phase polymeric additive.
The two-phase polymeric additive of lead accumulator of the present invention can not use one kettle way to mix, and one is followed after need to stocking up
Prepared by fixed process, the preparation method includes：
1) described emulsifying agent is divided into two parts, it is standby；
2) described component A and described B component are thoroughly mixed and uniformly, then add described component C, fully
It is uniformly mixed；
3) described a copy of it emulsifying agent is used to adjust the HLB of mixture obtained by step 2) to 10~14；
4) HLB of another described emulsifying agent is adjusted to 10~14, adds described industrial pure water, be sufficiently mixed
It is even, described aerosil is then added, is thoroughly mixed uniformly；In this step, including by adjustment contain emulsifying agent
Industrial pure water and the ratio of aerosil adjust the clarity of final mixture；
5) mixture that step 3) obtains is well mixed with the mixture that step 4) obtains in being sufficiently stirred, that is, obtained
Two-phase polymeric additive of the present invention.In this step, it is included in blend step 3) before obtained mixture, with described
Alkaline regulator adjusts the pH value of mixture obtained by step 4) to 8-10.
Above-mentioned steps 1) in, the quantitative ratio for industrial pure water being divided into two parts requires looser, also with being stirred
The operating condition of step is related (such as the environment temperature and environmental stress being stirred), in general, the emulsifier
As long as reach the HLB regulation targets of the step 3) and step 4).
Above-mentioned steps 2) in, the preferable silicone combinations objects system of mobility can be formed under normal condition.
Above-mentioned steps 3) O/W type emulsifying agents mainly are used, when the emulsion stability deficiency of one-component emulsifying agent is, it is necessary to carry
When rising emulsion stability, recommend the two or more compoundings using foregoing emulsifying agent.
Above-mentioned steps 4) in, before aerosil is disperseed with industrial pure water, add and HLB is adjusted to 11~14
Emulsifying agent, it is therefore an objective to make the effect of the scattered aerosil of industrial pure water more preferable；When obtained mixture clarity deficiency is (logical
It is often big with apparent viscosity), it can be adjusted by the material ratio of industrial pure water of the regulation containing emulsifying agent and aerosil
The clarity of mixture.
Above-mentioned steps 5) pH value by mixture obtained by step 4) that includes is adjusted to 8-10, and it is in order in the basic conditions
Make the mixed effect of two kinds of mixtures more preferable.In step 5) operation, recommend mixture obtained by step 3) being slowly injected into step
4) mixture obtained, and persistently stirred in being slowly injected into.In order that the quality of described two-phase polymeric additive is more
It is good, conventional filtration technique can also be increased afterwards in step 5)；If desired for long-term storage, can continue in step 5) appropriate addition afterwards
Alkaline regulator 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 two-phase polymeric additive of lead accumulator of the present invention is a kind of typical micro- dispersoid, is fabricated to
Work(degree associates larger with preparation method, and its production effect can be carried out by Tyndall (Tyndall) phenomenon to colloidal dispersion
Examine；It is known in industry, wavelength be 400-700mm light by microdispersed colloidal dispersion when, if dispersed colloid
Particle diameter, which is less than lambda1-wavelength, to be scattered, and current general experiment conclusion is：When the particle of colloidal dispersion system is straight
During footpath≤94nm, luminous intensity is hit in scattering and the biquadratic of wavelength is inversely proportional.The Tyndall of prepared two-phase polymeric additive shows
As obvious, illustrate that the making of this two-phase polymeric additive reaches Technology design target；Conversely, two made gatherings can be verified
It is unsuccessful to close additive system.
More deep personnel are studied for this area, and above-mentioned preparation method can be carried out etc. by adjusting mixed process completely
With replacement, but the change of operating process condition easily makes made two-phase polymeric additive produce isomers, influences two and meets
Close electrochemistry effect that additive is added after sulfuric acid liquid.It is different in the specific implementation of two-phase polymeric additive of the present invention
Selection and feed intake married operation, under the premise of as final mixture Stabilized, it is possible that clarity and electrochemistry work(
The contradiction of effect, the latter are often related to the aobvious state degree of Tyndall phenomenon.When can'tting eat one's cake and have it, recommend electrochemistry effect more excellent
Refinement formula and technique.
When this two-phase polymeric additive is mixed with other conventional additives, it is necessary first to when paying attention to mixed with other additives
Whether appearance is precipitated or viscosity increases to and is difficult to be filled into inside lead accumulator, while the lead that use other additives with must be stored
Battery performance is completely examined, and the mixtures' ratio with other additives is determined with cost performance.
The electrolyte of lead accumulator sulfuric acid liquid is prepared with two-phase polymeric additive of the present invention, filling lead stores
Battery has the obvious technical advantage of following items：
1st, the coupling of inorganic aerosil and silicone composition is stable, is added into the sulfuric acid liquid tool of lead accumulator
The double technique advantage of standby aerosil colloid and silicone composition colloid；
2nd, after the aggregation colloid 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
A kind of target is designed to add in lead accumulator sulfuric acid liquid, the two of the anti-softening ability of positive active material can be increased
Phase-polymerization additive, in terms of 100 parts by volume, component and content are the two-phase polymeric additive：
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 7 parts by volume；
B component：Viscosity be 1000 pas methyl-silicone oil, 7 parts by volume；
Component C：15wt% methyl silicate, 56 parts by volume；
Industrial pure water：26.5 parts by volume；
Aerosil：3 parts by volume (scaled value of weight/proportion)；
The parts by volume of emulsifying agent 0.5：From span 20 and Tween 80, wherein span 20 is for 0.1 parts by volume, and Tween 80 is for 0.3
Parts by volume, actual amount can adjust, to realize that the HLB of intermediate is adjusted to target.
Wherein, alkaline regulator selects sodium hydroxide, is prepared after completing stock using following process：
1) emulsifying agent is divided into two parts first, a copy of it compounds span 20 based on Tween 80, and HLB is adjusted to 12；Separately
The HLB of a Tween 80 and span 20 for adjustment intermediate.
2) component A of 7 parts by volume and the B component of 7 parts by volume are thoroughly mixed uniformly, then add 56 volume
The component C of part, it is thoroughly mixed uniformly；
3) use another described Tween 80 and span 20 emulsifying agent to compound, the HLB of mixture obtained by step 2) is adjusted
Save to 12；
4) HLB described in step 1) is adjusted to the industrial pure water of 12 a copy of it emulsifying agent 26.5 parts by volume of addition,
3 parts by volume aerosils are added after well mixed, are stirred 20 minutes；
5) pH value of mixture obtained by step 4) is adjusted to 11 with described sodium hydroxide, then, step 3) obtained
Mixture be slowly injected into the mixture that step 4) obtains, be thoroughly mixed during being slowly injected into uniformly, gained mixes
Compound is two-phase polymeric additive of the present invention.
Above-mentioned preparation method is stirred at normal temperatures and pressures, and the two-phase polymeric additive of gained need to such as be deposited for a long time, can
The described sodium hydroxide of appropriate addition adjusts its pH value to 12.The two-phase polymeric additive that the present embodiment obtains can be used as one kind
The wide spectrum additive of lead accumulator sulfuric acid liquid, different proportion is added according to different purposes.
Embodiment 2
Two-phase polymeric additive that embodiment 1 is obtained and density are 1.245 lead accumulator sulfuric acid liquid by volume 1：99
It is well mixed, the colloidal electrolyte polymerizeing as a kind of two-phase polymeric additive with sulfuric acid liquid.
The colloidal 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, turn into a resistant to elevated temperatures outdoor energy storage colloid plumbic storage battery.Two phase-polymerizations of the present embodiment
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 store lead
The effect that battery 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 0.5% of the extraordinary colloidal electrolyte volume total amount, and industry is generally accepted, and one is added in colloidal electrolyte
Determine the anhydrous sodium sulfate of content, electrolyte electrochemical activity can be lifted, reduce the internal resistance of colloid plumbic storage battery, lift leaching colloidal
The charge acceptance of battery.
Embodiment 3
In embodiment 1, aerosil is 2 parts by volume in the content of the two-phase polymeric additive, the present embodiment
Be 4 parts by volume by aerosil increase, i.e., the total amount of two-phase polymeric additive is 102 parts by volume by the increase of 100 parts by volume,
Remaining component and content are constant, and preparation method is same as Example 1.
Typically contrast effect test result on probation is：Silicone composition is different from the proportioning of aerosil, and two
Phase-polymerization additive can show different electrochemical properties, when two-phase polymeric additive is using silicone composition to be main, lead
The income that battery can obtain and reduce internal resistance, increase capacity；And when increasing the mixed proportion of aerosil, lead accumulator
The cycle charge-discharge life time decay shown is more steady.
The two-phase polymeric additive of the present embodiment is with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions is used, and circulation is filled
The life-span effect of electric discharge is better than embodiment 2.
Embodiment 4
Another electrolysis additive for adapting to the lead accumulator that long-term floating charge system uses is designed, its silicone composition
Component and content are in terms of 100 parts by volume：
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 oil, 1 parts by volume；
Component C：50wt% methyl silicate, 8 parts by volume；
Industrial pure water：74.5 parts by volume；
Aerosil：15 parts by volume；
The parts by volume of emulsifying agent 0.5：Compounded from span 40 and Tween 80, wherein span 40 is standby for 0.1 parts by volume, Tween 80
0.4 parts by volume, actual amount can adjust, to realize that the HLB of intermediate is adjusted to target.
Prepared after completing stock using following process：
1) emulsifying agent is divided into two parts, a copy of it compounds span 40 based on Tween 80, and HLB is adjusted to 14；Another
Tween 80 and span 40 are for adjusting the HLB of intermediate.
2) component A of 1 parts by volume and the B component of 1 parts by volume are thoroughly mixed uniformly, then add 8 volume
The component C of part, it is thoroughly mixed uniformly；
3) use another described Tween 80 and span 20 emulsifying agent to compound, the HLB of mixture obtained by step 2) is adjusted
Save to 14；
4) to it is described based on Tween 80, compounding span 40 make HLB be 14 a copy of it emulsifying agent addition 74.5 volumes
The industrial pure water of part, the aerosil of 15 parts by volume is added after well mixed, the process for mixing aerosil uses
Reactor, 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,
Persistently stir 30 minutes；If this step mixture clarity deficiency or viscosity are bigger than normal, by adjusting the technical pure containing emulsifying agent
The ratio of water and aerosil adjusts the clarity of mixture.
5) mixture obtained by step 3) is slowly injected into the mixture that step 4) obtains, during being slowly injected into fully
It is uniformly mixed, gained mixture is filtered, it is two-phase polymeric additive product to take filtrate.
Content of the present embodiment because of aerosil in two-phase polymeric additive is higher, is made with suitable after sulfuric acid liquid
Large Copacity lead accumulator, it is especially suitable for the outdoor energy storage lead accumulator for making long-term floating charge state.
Embodiment 5
The two-phase combined additive that embodiment 1 is obtained uses the homogenizing processing of high-speed emulsifying machine, described high speed breast
The homogenizing rotary speed of change machine is more than 20000 revs/min, after the homogenized deep processing processing of the two-phase combined additive, is with density
1.20 lead accumulator sulfuric acid liquid by volume 1：9 mixing are uniformly dispersed, and turn into a kind of and repair positive electode of lead battery active matter
The specialist additive of matter, market are 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. the two-phase polymeric additive of a kind of lead accumulator, it is characterised in that described two-phase polymeric additive is based on 100 bodies
Product 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 3000,1~7 parts by volume；
B component：Viscosity is less than the organic silicone oil of 2000 pas, 1~7 parts by volume；
Component C：10%-50wt% methyl silicate, 5~80 parts by volume；
Industrial pure water：10~88 parts by volume；
Aerosil：3~15 parts by volume；
The parts by volume of emulsifying agent 0.1~0.5, described emulsifying agent include the one or more of following material：Twain series emulsifier,
Span series emulsifying agent, triethanolamine, sodium carboxymethylcellulose, polyvinyl alcohol.
2. the two-phase polymeric additive of lead accumulator according to claim 1, it is characterised in that the component A siloxanes
R contained by side base includes H, OH, SO2H、NH2、CH3Or other unsaturated hydrophilic active groups.
3. the two-phase polymeric additive of lead accumulator according to claim 1, it is characterised in that the B component it is organic
Silicone oil includes methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, cyanoethyl methyl polysiloxane or containing other
The organic silicone oil of organic group.
4. the two-phase polymeric additive of lead accumulator according to claim 1, it is characterised in that two described phase-polymerizations add
Agent is added to be additionally included in the alkaline regulator that preparation process is used to adjust mixture pH value.
5. a kind of preparation method of the two-phase polymeric additive based on any lead accumulator of Claims 1 to 4, including：
1) described emulsifying agent is divided into two parts, it is standby；
2) described component A and described B component are thoroughly mixed and uniformly, then add described component C, be sufficiently stirred
It is well mixed；
3) described a copy of it emulsifying agent is used to adjust the HLB of mixture obtained by step 2) to 10~14；
4) HLB of another described emulsifying agent is adjusted to 10~14, adds described industrial pure water, be sufficiently mixed uniformly,
Then described aerosil is added, is thoroughly mixed uniformly；In this step, including by adjusting the work containing emulsifying agent
The ratio of industry pure water and aerosil adjusts the clarity of final mixture；
5) mixture that step 3) obtains is well mixed with the mixture that step 4) obtains in being sufficiently stirred, that is, obtains this hair
Bright described two-phase polymeric additive.In this step, it is included in blend step 3) before obtained mixture, with described alkalescence
Regulator adjusts the pH value of mixture obtained by step 4) to 8-10.
6. the lead storage battery electrolytic solution containing any two-phase polymeric additive of Claims 1 to 4 repairs liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710791653.XA CN107565173A (en) | 2017-09-05 | 2017-09-05 | A kind of two-phase polymeric additive of lead accumulator and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710791653.XA CN107565173A (en) | 2017-09-05 | 2017-09-05 | A kind of two-phase polymeric additive of lead accumulator and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107565173A true CN107565173A (en) | 2018-01-09 |
Family
ID=60979319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710791653.XA Withdrawn CN107565173A (en) | 2017-09-05 | 2017-09-05 | A kind of two-phase polymeric additive of lead accumulator and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107565173A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312331A (en) * | 2001-02-23 | 2001-09-12 | 刘粤荣 | Organic high molecular composite for accumulator and its preparation method |
| CN1383225A (en) * | 2001-04-23 | 2002-12-04 | 刘粤荣 | Electrolyte or chemical liquid composition for lead-acid accumulator and its preparing process |
| CN104091968A (en) * | 2014-07-31 | 2014-10-08 | 浙江天能电池江苏新能源有限公司 | Gel electrolyte capable of prolonging service life of lead-acid battery |
| CN104538679A (en) * | 2015-01-14 | 2015-04-22 | 山东大学 | Application of organosilicon compound serving as additive in colloid storage battery |
-
2017
- 2017-09-05 CN CN201710791653.XA patent/CN107565173A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312331A (en) * | 2001-02-23 | 2001-09-12 | 刘粤荣 | Organic high molecular composite for accumulator and its preparation method |
| CN1383225A (en) * | 2001-04-23 | 2002-12-04 | 刘粤荣 | Electrolyte or chemical liquid composition for lead-acid accumulator and its preparing process |
| CN104091968A (en) * | 2014-07-31 | 2014-10-08 | 浙江天能电池江苏新能源有限公司 | Gel electrolyte capable of prolonging service life of lead-acid battery |
| CN104538679A (en) * | 2015-01-14 | 2015-04-22 | 山东大学 | Application of organosilicon compound serving as additive in colloid storage battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107464959A (en) | A kind of polymeric additive for lead accumulator and preparation method thereof | |
| CN105669910B (en) | A kind of polycarboxylic-acid cement grinding aid and preparation method | |
| CN105375068B (en) | A kind of colloidal electrolyte of lead acid accumulator and compound method | |
| CN101838934A (en) | Soaking agent for surface processing of glass fiber filter cloth and preparation method thereof | |
| CN101071859A (en) | Lithium cell anode active substance, anode dressing and its preparing method | |
| CN1383225A (en) | Electrolyte or chemical liquid composition for lead-acid accumulator and its preparing process | |
| CN1157442C (en) | Organic polymer composition for lead accumulator and its prepn and use | |
| CN1152923C (en) | Organic high molecular composite for accumulator and its preparation method | |
| CN107623146A (en) | A kind of two-phase combined additive, purposes and preparation method thereof | |
| JP2013191537A (en) | Paste composition for microporous layer formation, and method of manufacturing the same | |
| CN106046395A (en) | Ternary copolymerized segmented organic silicone oil microemulsion and preparation method and application thereof | |
| CN109332087A (en) | A kind of lithium ion battery separator and preparation method thereof and apparatus for coating | |
| CN110467212A (en) | A kind of method of modifying of nano barium sulfate | |
| CN107394281A (en) | A kind of additive package of lead storage battery electrolytic solution and preparation method thereof | |
| CN107546424A (en) | A kind of combined additive of lead storage battery electrolytic solution and preparation method thereof | |
| CN107565173A (en) | A kind of two-phase polymeric additive of lead accumulator and preparation method thereof | |
| CN107611488A (en) | A kind of polymeric additive of lead accumulator and preparation method thereof | |
| CN107611496A (en) | A kind of combined additive for lead accumulator and preparation method thereof | |
| CN107611494A (en) | A kind of two-phase for lead accumulator mixes polymers additive and preparation method thereof | |
| CN107579290A (en) | A kind of two-phase compositions additive, purposes and preparation method thereof | |
| CN107565175A (en) | A kind of two-phase compositions of lead accumulator and preparation method thereof | |
| CN107546422A (en) | A kind of additive package of lead accumulator and preparation method thereof | |
| CN107579286A (en) | A kind of mixed poly- additive of lead accumulator and preparation method thereof | |
| CN107611489A (en) | A kind of mixed poly- additive of lead storage battery electrolytic solution and preparation method thereof | |
| CN107611492A (en) | A kind of two-phase of lead accumulator mixes poly- additive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180109 |
|
| WW01 | Invention patent application withdrawn after publication |