CN107546425A - A kind of polymeric additive of lead storage battery electrolytic solution and preparation method thereof - Google Patents
A kind of polymeric additive of lead storage battery electrolytic solution and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of polymeric additive of lead storage battery electrolytic solution and preparation method thereof, described 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；The parts by volume of industrial pure water 66.5~95.75；The parts by volume of aerosil 2~17；The water miscible parts by volume of polyvinyl alcohol 0.2~2；The parts by volume of emulsifying agent 0.05~0.5；Described 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, there is the effect of helping 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 polymerization addition of more particularly to a kind of lead storage battery electrolytic solution
The material of agent, formula and preparation method thereof.
Background technology
Lead accumulator abbreviation battery, in high-power/Large Copacities such as electrically propelled traction vehicle, car and boat starting, communication equipment station, energy storage
Field occupies empery status；In recent years with photovoltaic generation industry, the development of wind power industry, market common requirements great Rong
The battery of amount makees energy storage with applying mechanically, but conventional battery shows short life in use out of doors, and it is higher to discard rate, constrains
The business application of photovoltaic energy storage system.Industry is generally accepted, and appropriate colloidal substance is added in the sulfuric acid liquid of lead accumulator, can
Effectively lift the life-span used out of doors.
The colloid that lead accumulator industry tradition uses is aerosil, passes through industrial pure water or other solvents during use
Method fully liquefies aerosil；In Chinese invention patent ZL01109623.3, one kind is disclosed by poly- elemental silicon
The silicone composition of oxygen alkane, methyl-silicone oil and thinned water mixing, said composition is mixed with sulfuric acid liquid gathers as lead accumulator
Electrolyte or forming liquid.Applied by ten several years, industry generally believes aerosil colloid and high molecular weight siloxane polymerization
Colloid is each has something to recommend him, and the former viscosity is high, manufacturability difference and lead accumulator decline without the income for reducing internal resistance, increasing capacity, but life-span
Subtract relatively steadily, the latter's viscosity is low, good manufacturability and lead accumulator can obtain the income for reducing internal resistance, increasing capacity, but stability
Not 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 for being simply used in mixed way two class colloids and unsuccessful, technical reason is：Often
It is a kind of aqueous-phase material to advise aerosil colloid, but described silicone composition is a kind of hydrophily oil phase thing, incite somebody to action both
The fine dispersion system being simply mixed 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 after aerosil fully can be coupled with silicone composition, be added into sulfuric acid liquid to be lifted
The aggregation colloid additive of lead accumulator chemical property, lead accumulator is effectively extended outdoor service life, reduce and store
The discarded rate of 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 polymeric additive of lead storage battery electrolytic solution, described polymerization
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；
Industrial pure water：66.5~95.75 parts by volume；
Aerosil：2~17 parts by volume；
The water miscible parts by volume of polyvinyl alcohol 0.2~2, described water miscible polyvinyl alcohol be active matter content 8~
10% fluid 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 breast
Agent, Span series emulsifying agent, triethanolamine, sodium carboxymethylcellulose, polyvinyl alcohol.
In the content of above-mentioned polymeric additive, the aerosil parts by volume is the scaled value of its weight/proportion.
In the component of above-mentioned polymeric 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 above-mentioned polymeric additive, the B component organic silicone oil includes methyl-silicone oil, ethyl silicon oil, phenyl silicon
Oil, Methyl Hydrogen Polysiloxane Fluid or the organic silicone oil containing other organic groups.
The material and ratio range of polymeric additive based on above-mentioned lead storage battery electrolytic solution, present invention also offers one kind
Described stock up is fabricated to the preparation method of the polymeric additive, this method includes：
1) described industrial pure water is divided into two parts, described emulsifying agent is divided into 3 parts, standby；
2) described component A and described B component are thoroughly mixed uniformly；
3) HLB of a copy of it emulsifying agent is adjusted to 7~9, is added thereto a industrial pure water, added after well mixed
In the mixture that step 2) obtains, it is thoroughly mixed uniformly, then, will be mixed obtained by this step with another described emulsifying agent
The HLB of compound is adjusted to 10~14；
4) HLB of another part emulsifying agent is adjusted to 10~14, adds another industrial pure water, added after being well mixed
Enter described aerosil, be thoroughly mixed uniformly；
5) mixture obtained to step 4) adds described water miscible polyvinyl alcohol, is sufficiently mixed uniformly；
6) mixture that step 3) obtains is well mixed with the mixture that step 5) obtains in being sufficiently stirred, that is, obtained
It is of the present invention to mix poly- additive.
In the preparation method of above-mentioned polymeric additive, described step 4) also includes：By adjusting the industry containing emulsifying agent
The material ratio of pure water and aerosil come adjust gained mixture clarity.
Present invention also offers a kind of lead storage battery electrolytic solution containing above-mentioned polymeric additive or repair liquid.The electrolysis
The sulfuric acid liquid of liquid or reparation liquid using density as 1.05-1.35 is key component, body of the polymeric additive in the electrolyte
Product content 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 polymeric additive produced with the material prescription and preparation technology is low, is added into sulphur
Gel is slow after acid solution, is typically added into sulfuric acid liquid a few hours and still meets technological requirement to lead accumulator routine liquid filling, and leads to
It is good with property, it 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 shortcomings that polymeric additive of the present invention can overcome aerosil colloid and silicone composition colloid, passes through
Above-mentioned material prescription and preparation method, polymerizeing of can obtaining that inorganic aerosil and silicone composition be fully coupled add
Add agent, the additive, which adds sulfuric acid liquid, has percdation ability to chloride plate, can slow down positive active material because of sulphur
Lattice avalanche speed caused by lead plumbate oxidationreduction, cycle life is set to give extension (the main reason for lead accumulator end-of-life
Caused by positive material(PAM) softening, to account for end-of-life probability 80%), now described polymeric additive can be considered a kind of
The reinforcing agent used for positive pole.Similarly, the capacity attenuation lead accumulator of confirmation positive material(PAM) softening, the additive are added
Enter sulfuric acid liquid and can be considered a kind of reparation liquid.
A kind of polymeric 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 polymeric additive of the present invention, can produce a kind of has work(to lead accumulator
The polymeric additive of effect, the polymeric 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, 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 polymeric 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 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, a kind of two-phase interface theory of electrochemistry thinks, (A+B) copolymerization is formed
Special compound bone add sulfate liquid system and be more beneficial for ion cluster gathering and close directed movement, increase ion transition in the channel
Ability, be advantageous to be formed the absorption electric double layer of dynamic equilibrium in electrode and electrolyte two-phase interface, strengthen ion in electrode table
The activation energy of face 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 polymeric 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 emulsifying agent is used to prepare the hydrophilic lipophilic balance (HLB) of polymeric additive procedure regulation intermediate.
Such as the experiences that are about worth of HLB are estimated according to water-soluble method, the HLB of (A+B) copolymer being typically prepared works as use 7~9
, it is necessary to which the HLB of two intermediates is adjusted to oil respectively when industrial pure water is scattered, operation need to mix poly- with aqueous-phase material again in next step
Phase/aqueous phase adaptation value.Described emulsifying agent is the common articles for use of pharmacy/chemical industry, such as tween (polyoxyethylene sorbitan mountain
Pears alcohol fatty acid ester) it is a kind of nonionic surface active agent, it is widely used as oil-in-water (O/W) type emulsifying agent and oil phase substance
Solubilizer, the stabilization that can increase emulsifying agent is shared with other emulsifying agents such as sapn (sorbitan fatty acid ester) class emulsifying agent
Property, and spans is widely used as Water-In-Oil (W/O) type emulsifying agent and the solubilizer of aqueous phase substance.The HLB of various emulsifying agents
It is each variant, even same component emulsifying agent also can influence its HLB because of content, purity difference, according to right when specifically used
HLB requirements different and it is preferred that compound regulation, it is such as required with tween emulsifier type and the compounding regulation of spans emulsifying agent
HLB。
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 polyvinyl alcohol (PVA) is a kind of organic compound, and being uniquely can be by bacterium as carbon source and using energy source
Polyvinyl, belong to a kind of Biodegradable polymer material, and can be mass produced by Non oil-based route, eating
There is unique advantage in terms of product, Key works Drug packing.PVA is a kind of excellent organic matter of great secondary development potentiality simultaneously, such as base
In solwution method, thin-film material can be prepared by casting film-forming.Application viewpoint of the lead accumulator industry to PVA is concentrated mainly on water-soluble
The polyvinyl alcohol of property, it is intended to which add strengthens the electro-chemical activity of lead accumulator in right amount in sulfate liquid system；It is of the present invention
Water miscible polyvinyl alcohol is the fluid product of active matter content 8~10%, and it is main additive package of the present invention
It is solidifying after the emulsion stability and mix sulphur acid solution for improving additive package of the present invention as dispersant and emulsion stabilizer
Glue effect.
The raw material of above-described polymeric 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 polymeric additive is influenced whether, the polymeric 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 polymeric additive.
The polymeric additive of lead storage battery electrolytic solution 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 industrial pure water is divided into two parts, described emulsifying agent is divided into 3 parts, standby；
2) described component A and described B component are thoroughly mixed uniformly；
3) HLB of a copy of it emulsifying agent is adjusted to 7~9, is added thereto a industrial pure water, added after well mixed
In the mixture that step 2) obtains, it is thoroughly mixed uniformly, then, will be mixed obtained by this step with another described emulsifying agent
The HLB of compound is adjusted to 10~14；
4) HLB of another part emulsifying agent is adjusted to 10~14, adds another industrial pure water, added after being well mixed
Enter described aerosil, be thoroughly mixed uniformly；
5) mixture obtained to step 4) adds described water miscible polyvinyl alcohol, is sufficiently mixed uniformly；
6) mixture that step 3) obtains is well mixed with the mixture that step 5) obtains in being sufficiently stirred, that is, obtained
It is of the present invention to mix poly- additive.
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), and in general, the step 3) is to step
The industrial pure water that rapid 2) gained mixture adds, can make mixture obtained by step 2) form the preferable liquid of mobility,
More industrial pure water remains step 4) operation.
Above-mentioned steps 3) in, before this using w/o type emulsifying agent, O/W type emulsifying agents are used afterwards, the emulsifying agent of one-component is not
This pair of HLB regulation requirement can be met, the two or more compoundings of foregoing emulsifying agent can be used.
The optimization operation of step 4) also includes the material by industrial pure water of the regulation containing emulsifying agent and aerosil
Ratio adjusts the clarity of mixture, when obtained mixture clarity deficiency (big generally with apparent viscosity), can pass through
Described material ratio adjusts the clarity of mixture, makes the quality of mixture more preferably.
Above-mentioned steps 6) in, recommend mixture obtained by step 3) being slowly injected into the mixture that step 5) obtains, and
Persistently stirred in being slowly injected into.In order that the quality of polymeric additive is more preferable, conventional filtration can be increased after step 5)
Technique.The polymeric additive, if desired for long-term storage, can continue to add alkaline regulator in right amount for example after completing to prepare
Sodium hydroxide adjusts its pH value to more than 10.
Being stirred described in method made above can be carried out at normal temperatures and pressures, and described is stirred including rotation
Formula stirring, the shearing stirring of periodicity or corner cut at random, it can also heat, reaction is helped using compressive reaction kettle, such as mixed
The temperature that mixture is kept during being stirred of compound is 75 DEG C ± 15 DEG C；When adding reaction pressure to mix using reactor
When, kettle pressure is no more than 25MPa.
The polymeric additive of lead storage battery electrolytic solution 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 phenomenon of prepared polymeric additive is bright
It is aobvious, illustrate that the making of this polymeric additive reaches Technology design target；Conversely, made polymeric additive system can be verified
It is unsuccessful.
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；Such as first operating procedure 4) and step 5) operating procedure 2 afterwards) and the sequential replacement sheerly stocked up of step 3)；In another example
When the mobility of mixture obtained by the step 2) is good enough, step 3) is merged into step 4) and step 5) operates, then again with
The mixture that step 2) obtains is mixed poly-, though the preparation method of this kind of equivalent substitution is also operable, easily produces isomers, can shadow
Ring electrochemistry effect of polymeric additive.
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 polymeric additive is obvious, when mixed with other conventional additives, it is necessary first to pay attention to and its
Whether his additive occurs precipitating when mixed or viscosity increases to and is difficult to be filled into inside lead accumulator, meanwhile, set as one kind
Count additive of the target for lifting performance of lead-acid battery, it is necessary to which the performance of lead-acid battery for using other additives with is examined comprehensively
Test, the mixtures' ratio with other additives is determined with cost performance.
The electrolyte of lead accumulator sulfuric acid liquid, filling lead accumulator are prepared with polymeric 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 polymeric 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 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 poly- of the anti-softening ability of positive active material can be increased
Additive is closed, in terms of 100 parts by volume, component and content are the 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；
Industrial pure water：83 parts by volume；
Aerosil：2 parts by volume (scaled value of weight/proportion)；
Water miscible polyvinyl alcohol：0.5 parts by volume
The parts by volume of emulsifying agent 0.5：From span 20 and Tween 80, wherein span 20 is for 0.2 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 design object.
After completing stock, prepared using following process：
1) 83 parts by volume industrial pure waters are divided into 60 parts by volume and 23 parts by volume first：Each point described of two kinds of emulsifying agents
For 3 parts, a copy of it compounds Tween 80 based on span 20, and HLB is adjusted to 8；Another compounds sapn based on Tween 80
20, HLB are adjusted to 12；A Tween 80 is stayed for adjusting HLB.
2) component A of 7 parts by volume and the B component of 7 parts by volume are thoroughly mixed uniformly；
3) a copy of it emulsifying agent that HLB is 8 is added to the industrial pure water of 60 parts by volume, step is added after being well mixed
In the rapid mixture 2) obtained, it is sufficiently stirred, then uses described Tween 80 emulsifying agent to adjust the HLB of mixture obtained by this step
Save to 12；
4) another emulsifying agent that HLB is 12 is added to the industrial pure water of 23 parts by volume, 2 body is added after well mixed
Product part aerosil, is stirred more than 30 minutes；
5) mixture obtained to step 4) adds the water miscible polyvinyl alcohol of 0.5 parts by volume, is sufficiently mixed uniformly；
6) mixture for obtaining step 3) is slowly injected into the mixture that step 5) obtains, and is filled during being slowly injected into
Divide and be uniformly mixed, gained mixture is polymeric additive of the present invention.
The present embodiment preparation method is stirred at normal temperatures and pressures, and the polymeric additive of gained can be used as a kind of lead electric power storage
The wide spectrum additive of pond sulfuric acid liquid, different proportion is added according to different purposes.The polymeric additive of gained need to such as be deposited for a long time,
The alkaline regulator such as sodium hydroxide of addition can be added in right amount to adjust its pH value to 12.
Embodiment 2
Polymeric additive that embodiment 1 is obtained and density are 1.245 lead accumulator sulfuric acid liquid by volume 1：99 mixing
Uniformly, poly- colloidal electrolyte is mixed as a kind of silicone composition, silica and 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.The polymerization addition of the present embodiment
Agent 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 lead accumulator
It is obvious to obtain the effect for reducing internal resistance, increasing 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 polymeric additive, and the present embodiment is by gas
Aerosil increase be 6 parts by volume, i.e., it is 104 parts by volume that the total amount of polymeric additive is increased by 100 parts by volume, remaining component
Constant with content, preparation method is same as Example 1.
Typically contrast effect test result on probation is：Silicone composition is different from the proportioning of aerosil, gathers
Different electrochemical properties can be shown by closing additive, and when polymeric 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 polymeric additive of the present embodiment is with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions uses, cycle charge-discharge
Life-span effect it is better than embodiment 2；The polymeric additive of the present embodiment is with volume ratio 1：10 mix sulphur acid solutions, by 1ml/10Ah
Quantify and be added into through being judged as positive material(PAM) softening and inside the lead accumulator of capacity attenuation, through known to industry plus negative
Press technique, by secondary formation charging technique, the positive plate of softening can be made to live after the inner panel group of lead accumulator is evenly distributed
Property material harden again, make lead accumulator recover capacity.
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；
Industrial pure water：79.95 parts by volume；
Aerosil：17 parts by volume；
Water miscible polyvinyl alcohol：1 parts by volume
The parts by volume of emulsifying agent 0.05：It is standby for 0.01 parts by volume, Tween 80 from span 40 and Tween 80, wherein span 40
0.04 parts by volume, actual amount can adjust, to realize that the HLB of intermediate is adjusted to design object.
Prepared after completing stock using following process：
1) 79.95 parts by volume industrial pure waters are divided into 9.95 parts by volume and 70 parts by volume：Two kinds of described emulsifying agents are each
It is divided into 3 parts, a copy of it compounds Tween 80 based on span 40, and HLB is adjusted to 7；Another is based on Tween 80, compounding department
Disk 40, HLB is adjusted to 13；A Tween 80 is stayed for adjusting HLB.
2) component A of 1 parts by volume and the B component of 1 parts by volume are thoroughly mixed uniformly；
3) a copy of it emulsifying agent that HLB is 7 is added to the industrial pure water of 9.95 parts by volume, added after well mixed
In the mixture that step 2) obtains, it is thoroughly mixed uniformly, then uses described Tween 80 emulsifying agent will be mixed obtained by this step
The HLB of compound is adjusted to 13；
4) another emulsifying agent that HLB is 13 is added to the industrial pure water of 70 parts by volume, described 17 are added after well mixed
The aerosil of parts by volume, the process for mixing aerosil are pressurizeed and heated using reactor and help reaction, and kettle pressure is
20MPa, it is 75 DEG C ± 10 DEG C that the mixture temperature in kettle is kept in using reactor mixed process, is persistently mixed 30 minutes；
If this step mixture clarity deficiency or viscosity are bigger than normal, by adjusting industrial pure water and aerosil containing emulsifying agent
Material ratio adjust the clarity of mixture.
5) mixture obtained to step 4) adds the water miscible polyvinyl alcohol of 1 parts by volume, is sufficiently mixed uniformly；
6) mixture for obtaining step 3) is slowly injected into the mixture that step 5) obtains, during being slowly injected into fully
It is uniformly mixed, gained mixture is filtered, filtrate is described polymeric additive.
Content of the present embodiment because of aerosil in polymeric additive is higher, and great Rong is made with suitable after sulfuric acid liquid
Lead accumulator is measured, is especially suitable for the outdoor Large Copacity energy storage lead accumulator for making long-term floating charge.
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 polymeric additive of lead storage battery electrolytic solution, it is characterised in that based on the polymerization addition described in 100 parts by volume
Agent, 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；
Industrial pure water：66.5~95.75 parts by volume；
Aerosil：2~17 parts by volume；
The water miscible parts by volume of polyvinyl alcohol 0.2~2, described water miscible polyvinyl alcohol are active matter content 8~10%
Fluid 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 polymeric additive of lead storage battery electrolytic solution 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 polymeric additive of lead storage battery electrolytic solution 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 or the organic silicone oil containing other organic groups.
4. a kind of preparation method based on any described polymeric additive of claims 1 to 3, including：
1) described industrial pure water is divided into two parts, described emulsifying agent is divided into 3 parts, standby；
2) described component A and described B component are thoroughly mixed uniformly；
3) HLB of a copy of it emulsifying agent is adjusted to 7~9, is added thereto a industrial pure water, step is added after well mixed
2) in the mixture obtained, it is thoroughly mixed uniformly, then, with another described emulsifying agent by mixture obtained by this step
HLB adjust to 10~14；
4) HLB of another part emulsifying agent is adjusted to 10~14, adds another industrial pure water, institute is added after well mixed
The aerosil stated, it is thoroughly mixed uniformly；
5) mixture obtained to step 4) adds described water miscible polyvinyl alcohol, is sufficiently mixed uniformly；
6) mixture that step 3) obtains is well mixed with the mixture that step 5) obtains in being sufficiently stirred, that is, obtains this hair
Bright described mixed poly- additive.
5. according to the method for claim 4, it is characterised in that described step 4) also includes：Emulsifying agent is contained by adjustment
Industrial pure water and aerosil material ratio come adjust gained mixture clarity.
6. the lead storage battery electrolytic solution containing any polymeric additive of claims 1 to 3 repairs liquid.
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|---|---|---|---|---|
| CN1312331A (en) * | 2001-02-23 | 2001-09-12 | 刘粤荣 | Organic high molecular composite for accumulator and its preparation method |
| CN104218261A (en) * | 2014-08-15 | 2014-12-17 | 浙江天能电池江苏新能源有限公司 | Colloid electrolyte capable of improving service life of lead-acid cell |
| EP3021415A1 (en) * | 2014-11-13 | 2016-05-18 | F.I.A.M.M. S.P.A. | Additive for electrolyte of lead-acid batteries |
| US20170025681A1 (en) * | 2013-11-29 | 2017-01-26 | Gs Yuasa International Ltd. | Lead-acid battery |
| CN107464959A (en) * | 2017-08-30 | 2017-12-12 | 东莞恒量新能源科技有限公司 | A kind of polymeric additive for lead accumulator and preparation method thereof |
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2017
- 2017-08-30 CN CN201710761860.0A patent/CN107546425A/en not_active Withdrawn
Patent Citations (5)
| 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 |
| US20170025681A1 (en) * | 2013-11-29 | 2017-01-26 | Gs Yuasa International Ltd. | Lead-acid battery |
| CN104218261A (en) * | 2014-08-15 | 2014-12-17 | 浙江天能电池江苏新能源有限公司 | Colloid electrolyte capable of improving service life of lead-acid cell |
| EP3021415A1 (en) * | 2014-11-13 | 2016-05-18 | F.I.A.M.M. S.P.A. | Additive for electrolyte of lead-acid batteries |
| CN107464959A (en) * | 2017-08-30 | 2017-12-12 | 东莞恒量新能源科技有限公司 | A kind of polymeric additive for lead accumulator and preparation method thereof |
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Application publication date: 20180105 |