CN102208690A - Colloid electrolyte for lead-acid battery and preparation method thereof - Google Patents

Colloid electrolyte for lead-acid battery and preparation method thereof Download PDF

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CN102208690A
CN102208690A CN2011101237519A CN201110123751A CN102208690A CN 102208690 A CN102208690 A CN 102208690A CN 2011101237519 A CN2011101237519 A CN 2011101237519A CN 201110123751 A CN201110123751 A CN 201110123751A CN 102208690 A CN102208690 A CN 102208690A
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electrolyte
preparation
ludox
hydroxyethylcellulose
solution
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陈红雨
潘珂
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South China Normal University
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Abstract

The invention belongs to the technical field of colloid lead-acid battery electrolytes and relates to a novel colloid electrolyte for a lead-acid battery and a preparation method thereof. In the colloid electrolyte, a silica sol is taken as a gel and contains 0.001%-0.009% of hydroxyethyl cellulose. The preparation method comprises the following steps: 1, preparing a hydroxyethyl cellulose water solution with the mass percent of 0.05%-0.5%; 2, preparing silicon dioxide into a silica sol and adding the silica sol to a sulfuric acid solution as well as stirring; and 3, adding the hydroxyethyl cellulose water solution in the step 1 to the solution obtained in the step 2, and dispersing. The hydroxyethyl cellulose is adopted to be an additive of the silica solution colloid electrolyte, thus playing a thickening role in a pure silica solution electrolyte, avoiding the defect of hydration layering of the pure silica solution colloid electrolyte, improving the stability of the pure silica solution colloid electrolyte, inhibiting the colloid electrolyte from hydrogen evolution and oxygen evolution to reduce self discharge, increasing the discharge capacity of a lead negative electrode, improving the charge acceptance of the lead negative electrode, restraining sulfation of the negative electrode and being beneficial to prolonging the service life of the battery.

Description

A kind of lead acid accumulator colloidal electrolyte and preparation method thereof
Technical field
The present invention relates to the electrolytical technical field of gelled lead acid battery, particularly a kind of lead acid accumulator colloidal electrolyte and preparation method thereof of colloidal electrolyte.
Background technology
The lead acid accumulator development is the history in existing more than 150 year so far, though be that keffel is old but vigorous.According to 2004 annual datas statistics, lead acid accumulator accounts for more than 50% of total share of all secondary cells, has occupied the empery status of secondary cell.
Gelled lead acid battery is an innovating reform to traditional lead acid accumulator, because of colloidal electrolyte has that electrolyte does not flow, not leakiness acid, effectively reduce self discharge, prolong advantage such as battery useful life, colloid battery is widely used in electric power, telecommunications, the power supply system for communications, the military communication station, electric motor car, applications such as solar wind-energy accumulation power supply.
Lead acid accumulator comprises Ludox and aerosil with the colloidal electrolyte gel at present.Domestic preparation aerosil technology is very unripe, and product quality is not as external import.And the colloidal electrolyte viscosity with its preparation is very high, can't pour into battery with conventional method, needs to produce colloid storage battery with the can and the gel process of complexity.U.S. Johnson company, German Hagen company and Japanese Gs company etc. all once prepared colloidal electrolyte of lead acid accumulator with Ludox, but the overwhelming majority adopts aerosil now.From battery performance, the battery performance of glue that aerosil is joined is more excellent.But from domestic statistics, the gelled lead acid battery company that with the aerosil is gel because of the cost of material height, to the requirement height of production equipment, has restricted the development of aerosil colloid battery not at majority.Therefore consider from domestic national conditions, still have very long stretch to walk as the gel of electrolyte with Ludox.But cause battery not long useful life with colloidal electrolyte Yishui River hierarchies in battery charge and discharge process that Ludox is joined.
Existing colloidal electrolyte additive can improve the performance of battery to a certain extent, comprises inorganic additive and organic additive.
Inorganic additive commonly used has sulfate, phosphoric acid and boric acid etc.Magnesium sulfate, aluminum sulfate, cobaltous sulfate be as the coordination dopant, can with Pb 2+Form complex, this compound is unsettled in acid medium, makes the nonconducting lead sulfate dissolving of part turn back in the electrolyte, and these additives stop sulfation, can also suppress early stage capacity depletion, improve energy density and low-temperature startup performance.And in colloidal electrolyte, add SnSO 4Can prolong battery cycle life and inhibition capacity effectively descends.Many in addition scholars have also studied the possibility that adds phosphoric acid in gelled lead acid battery.Phosphoric acid is made additive, have different versions: have in the bibliographical information electrolyte phosphoric acid of adding can reduce the precipitation rate of oxygen on electrode, reduce the fluid loss of battery, reduce battery because electrolyte is dry and cause the possibility of inefficacy; But the adding that bibliographical information phosphoric acid also arranged is disadvantageous to the influence of the life of storage battery, and along with the increase of phosphorus acid content, this trend is more obvious.So whether phosphoric acid join in the storage battery life-span to battery as additive and exert an influence and be still waiting further research.
Though and researchers such as Badawy point out that the adding of phosphoric acid has stoped anodal self discharge, the adding of phosphoric acid has reduced the capacity of battery initial cycle, and when phosphoric acid concentration was very high, the cryogenic property of battery is very poor (to have reduced PbSO especially 4Be oxidized to PbO 2Speed), and replace phosphoric acid to improve PbO with boric acid 2/ PbSO 4The speed of redox couple increases the corrosion resistance of lead and alloy thereof, and has solved the problem that joins in the storage battery to be run into as additive with phosphoric acid.
Organic additive not only can change the character of colloidal electrolyte, also can improve the performance of battery.Because there are atoms such as N, O, A1 in the organic additive molecule, they can provide share electron pair, form coordinate bond with the silicon bonding, have changed the diameter of Spherical Volume structure of polymer, and forming similar build is the space network structure of macromolecular compound.This structure can better be wrapped up " Free water ", reduces the diffusion velocity of water, reduces self-discharge rate.Organic additive commonly used mainly is some high molecular polymers, as polyacrylamide, polyvinyl alcohol, AEO, dextrin, glycerine etc.Wherein polyacrylamide plays the effect that absorbs moisture, can be used as the aquation layering that stabilizer is alleviated colloidal electrolyte.Also useful ionic liquid is as the report of additives of lead-acid battery, and the adding of triethyl group hydrogen sulfate amine, dibutyl sulfuric acid hydrogen amine, benzyl hydrogen sulfate amine, 1-butyl-3-methylimidazole hydrogen sulfate amine plasma liquid can improve H 2And O 2Separate out overpotential, reduce water loss, and can accelerate PbSO 4Be transformed into PbO 2Speed and increase the utilance of positive active material; But it has increased the corrosion rate of electrode plate grid to a certain extent.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art; adding a certain amount of thickener at the Ludox colloidal electrolyte is again the hydroxyethylcellulose of colloid protective agent simultaneously; improve the layering of Ludox colloidal electrolyte aquation, improve glue stability, thereby improve the performance of colloid battery.
Invention realizes above-mentioned purpose by following scheme:
Invention provides a kind of novel lead-acid storage battery colloidal electrolyte, and described electrolyte is the Ludox electrolyte of Ludox electrolyte, and wherein contains hydroxyethylcellulose.The mass fraction of hydroxyethylcellulose in electrolyte is 0.001% ~ 0.009%, and preferred content is mass fraction 0.003%.
Contain silicon dioxide and sulfuric acid in the described Ludox electrolyte, the mass fraction of silicon dioxide net content in electrolyte is 4 ~ 6%; The density of sulfuric acid in electrolyte is 1.26 ~ 1.32g/mL.Invention provides the preparation method who prepares this colloidal electrolyte simultaneously, it is characterized in that may further comprise the steps:
(1) hydroxyethyl cellulose aqueous solution of preparation mass fraction 0.05% ~ 0.5%;
(2) silicon dioxide is configured as Ludox or employing finished silicon colloidal sol, joins in the sulfuric acid solution, stir;
(3) hydroxyethyl cellulose aqueous solution with step (1) joins in the solution of step (2) acquisition, and disperses.
Wherein, the concentration of the sulfuric acid solution that step (2) adopts is 40.6% ~ 51.1%, and the mass fraction of silicon dioxide is 39.5% ~ 40.5% in the Ludox.When Ludox is added sulfuric acid solution or afterwards, carry out stirring at low speed, rotating speed is 200 ~ 500r/min, preferred 300r/min.
After step (2) was finished, hydroxyethyl cellulose aqueous solution carried out high speed dispersion with high speed dispersor after adding in the solution of step (2), and rotating speed is 1400 ~ 1600r/min, and jitter time is 20 ~ 40min.Preferred rotating speed and jitter time are respectively 1500r/min and 30min.
Inventing preferred following scheme carries out:
1, preparation 0.05% hydroxyethylcellulose (HEC) aqueous solution;
Fill in the dispersion bucket of deionized water of certain volume one and to add a certain amount of hydroxyethylcellulose powder, limit edged stirring at low speed is heightened speed high-speed stirred certain hour after adding, and leaves standstill to treat to change over to after foam disappears the volumetric flask constant volume and get final product.Low speed is controlled at about 300r/min, and High-speed Control is at about 1500r/min, and jitter time is controlled at 20min.
2, the colloidal electrolyte of the different content HEC aqueous solution is added in preparation;
Preparation contains the Ludox colloidal electrolyte of HEC.The preparation method is as follows, according to the addition of material in the table 1, gets sulfuric acid solution, adds Ludox under stirring at low speed, adds the HEC aqueous solution again, after material adds, adopts at a high speed above-mentioned system is disperseed (jitter time 30 minutes).Low speed is controlled at about 300r/min, and High-speed Control is at about 1500r/min, and jitter time is controlled at 30min.In the colloidal electrolyte that is obtained, the content of hydroxyethylcellulose for be respectively 0.001%, 0.003%, 0.005%, 0.007%, 0.009%(w/w), the silicon dioxide net content is 5%(w/w), the content of sulfuric acid is 1.28g/mL.
The addition such as the table 1 of concrete material:
Each material addition of the different colloidal electrolytes of table 1
HEC content Contain 40%(w/w) the Ludox quality of silicon dioxide HEC (aq, 0.05%) volume The sulfuric acid volume
0% 50g 0mL 273mL(40.6%H 2SO 4)
0.001% 50g 8.2mL 260mL(41.5%H 2SO 4)
0.003% 50g 24.67mL 244mL(43.6%H 2SO 4)
0.005% 50g 41mL 229mL(45.8%H 2SO 4)
0.007% 50g 57.5mL 213mL(48.3%H 2SO 4)
0.009% 50g 74mL 198mL(51.1%H 2SO 4)
The colloidal electrolyte that is added HEC by method for preparing is applied in the gelled lead acid battery.Limited because of colleges and universities' experiment condition, only test the physical property and the electrochemical properties of colloidal electrolyte.Concrete method of testing: carry out flowability and viscosity test at once after the colloidal electrolyte preparation is finished; Treat that glue places its electrochemical properties of test and stability behind 24 hours gels.
The present invention relates to the compound method of colloidal electrolyte additive and this kind colloidal electrolyte, essence is to want to improve by the thickening power of additive hydroxyethylcellulose the drawback of pure silicon colloidal sol colloidal electrolyte Yishui River hierarchies.An amount of interpolation hydroxyethylcellulose (HEC) can obviously improve the electrochemical properties of glue, as: suppress liberation of hydrogen and analyse oxygen, reduce self discharge; Increase plumbous negative discharge capacity, improve cycle life; Reduce spontaneous generation lead sulfate under the plumbous negative pole laying state, be beneficial to charge transfer in the glue.
Other additives also can improve the colloidal electrolyte performance to some extent, also can realize the object of the invention.But can't realize the to a certain degree thickening of glue, overcome Ludox colloidal electrolyte aquation lamination.
Compared with prior art, the present invention has following beneficial effect:
1. adopt hydroxyethylcellulose to make the additive of Ludox colloidal electrolyte, to a certain extent pure silicon colloidal sol electrolyte has been played thickening power, can avoid the drawback of pure silicon colloidal sol colloidal electrolyte aquation layering, improve pure silicon colloidal sol colloidal electrolyte stability simultaneously.
2. add hydroxyethylcellulose in right amount, can obviously improve the physical property and the electrochemical properties of colloidal electrolyte: improve liquidity and improve glue stability; Also can effectively suppress electrolyte liberation of hydrogen oxygen evolution reaction, reduce self-discharge of battery, increase the discharge capacity and the charge acceptance of plumbous negative pole.
3. this additive cost is low, and raw material is easy to get, and it is simple and easy to do to join gluing method, and production equipment is not had specific (special) requirements, also can not increase the added burden that enterprise improves production equipment.
4. the colloid battery produced of this method, electrolyte property is good, stability is high, can be widely used in applications such as electric power, telecommunications, the power supply system for communications, the military communication station, electric motor car.
Description of drawings
Fig. 1 contains different content HEC(w/w for colloidal electrolyte) time colloidal electrolyte flowability
Fig. 2 contains different content HEC(w/w for colloidal electrolyte) time colloidal electrolyte viscosity
Fig. 3 contains different content HEC(w/w for colloidal electrolyte) time colloidal electrolyte analyse liquid measure
Fig. 4 contains different content HEC(w/w for colloidal electrolyte) time colloidal electrolyte colloid intensity
Fig. 5 contains different content HEC(w/w for colloidal electrolyte) time AC impedance figure under the colloidal electrolyte hydrogen-evolution overpotential
Fig. 6 contains different content HEC(w/w for colloidal electrolyte) time AC impedance figure under the colloidal electrolyte hydrogen-evolution overpotential
Fig. 7 contains different content HEC(w/w for colloidal electrolyte) time AC impedance figure under the colloidal electrolyte Open Circuit Potential
Fig. 8 contains different content HEC(w/w for colloidal electrolyte) time colloidal electrolyte cyclic voltammogram
Embodiment 1:
1. prepare mass fraction 0.05% hydroxyethyl cellulose aqueous solution
Fill in the dispersion bucket of deionized water of certain volume one and to add a certain amount of hydroxyethylcellulose powder, limit edged stirring at low speed is heightened speed high-speed stirred certain hour after adding, and leaves standstill to treat to change over to after foam disappears the volumetric flask constant volume and get final product.
2. the colloidal electrolyte that contains the HEC aqueous solution 0.001% is added in preparation;
Preparation contains the Ludox colloidal electrolyte of HEC.The preparation method is as follows, get the sulfuric acid solution of 260mL mass fraction 41.5%, adding 50g silicon dioxide quality mark is 40% Ludox (being produced by Shenzhen Hua Dao Industrial Co., Ltd.) under 300r/min stirs, the HEC aqueous solution that adds 8.2mL again, after treating that material adds, 1500r/min disperses (jitter time 30 minutes) to above-mentioned system.In the colloidal electrolyte that is obtained, the content of hydroxyethylcellulose is 0.001%(w/w), the silicon dioxide net content is 5%(w/w), the content of sulfuric acid is 1.28g/mL.
3. carry out flowability and viscosity test at once after the colloidal electrolyte preparation is finished; Treat that glue places its electrochemical properties of test and stability behind 24 hours gels.
Embodiment 2:
1. prepare mass fraction 0.05% hydroxyethyl cellulose aqueous solution
Fill in the dispersion bucket of deionized water of certain volume one and to add a certain amount of hydroxyethylcellulose powder, limit edged stirring at low speed is heightened speed high-speed stirred certain hour after adding, and leaves standstill to treat to change over to after foam disappears the volumetric flask constant volume and get final product.
2. the colloidal electrolyte that contains the HEC aqueous solution 0.003% is added in preparation;
The preparation method is as follows, get the sulfuric acid solution of 244mL mass fraction 43.6%, adding 50g silicon dioxide quality mark is 40% Ludox under 300r/min stirs, the HEC aqueous solution that adds 24.67mL again, after treating that material adds, 1500r/min disperses (jitter time 30 minutes) to above-mentioned system.In the colloidal electrolyte that is obtained, the content of hydroxyethylcellulose is 0.003%(w/w), the silicon dioxide net content is 5%(w/w), the content of sulfuric acid is 1.28g/mL.
3. carry out flowability and viscosity test at once after the colloidal electrolyte preparation is finished; Treat that glue places its electrochemical properties of test and stability behind 24 hours gels.
Embodiment 3:
1. prepare mass fraction 0.05% hydroxyethyl cellulose aqueous solution
Fill in the dispersion bucket of deionized water of certain volume one and to add a certain amount of hydroxyethylcellulose powder, limit edged stirring at low speed is heightened speed high-speed stirred certain hour after adding, and leaves standstill to treat to change over to after foam disappears the volumetric flask constant volume and get final product.
2. the colloidal electrolyte that contains the HEC aqueous solution 0.005% is added in preparation;
Preparation contains the Ludox colloidal electrolyte of HEC.The preparation method is as follows, get the sulfuric acid solution of 229mL mass fraction 45.8%, adding 50g silicon dioxide quality mark is 40% Ludox under 300r/min stirs, the HEC aqueous solution that adds 41mL again, after treating that material adds, 1500r/min disperses (jitter time 30 minutes) to above-mentioned system.In the colloidal electrolyte that is obtained, the content of hydroxyethylcellulose is 0.005%(w/w), the silicon dioxide net content is 5%(w/w), the content of sulfuric acid is 1.28g/mL.
3. carry out flowability and viscosity test at once after the colloidal electrolyte preparation is finished; Treat that glue places its electrochemical properties of test and stability behind 24 hours gels.
1. prepare mass fraction 0.05% hydroxyethyl cellulose aqueous solution
Fill in the dispersion bucket of deionized water of certain volume one and to add a certain amount of hydroxyethylcellulose powder, limit edged stirring at low speed is heightened speed high-speed stirred certain hour after adding, and leaves standstill to treat to change over to after foam disappears the volumetric flask constant volume and get final product.
2. the colloidal electrolyte that contains the HEC aqueous solution 0.007% is added in preparation;
Preparation contains the Ludox colloidal electrolyte of HEC.The preparation method is as follows, get the sulfuric acid solution of 213mL mass fraction 48.3%, adding 50g silicon dioxide quality mark is 40% Ludox under 300r/min stirs, the HEC aqueous solution that adds 57.5mL again, after material added, 1500r/min disperseed (jitter time 30 minutes) to above-mentioned system.In the colloidal electrolyte that is obtained, the content of hydroxyethylcellulose is 0.007%(w/w), the silicon dioxide net content is 5%(w/w), the content of sulfuric acid is 1.28g/mL.
3. carry out flowability and viscosity test at once after the colloidal electrolyte preparation is finished; Treat that glue places test and stability behind 24 hours gels.
Embodiment 4:
1. prepare mass fraction 0.05% hydroxyethyl cellulose aqueous solution
Fill in the dispersion bucket of deionized water of certain volume one and to add a certain amount of hydroxyethylcellulose powder, limit edged stirring at low speed is heightened speed high-speed stirred certain hour after adding, and leaves standstill to treat to change over to after foam disappears the volumetric flask constant volume and get final product.
2. the colloidal electrolyte that contains the HEC aqueous solution 0.009% is added in preparation;
Preparation contains the Ludox colloidal electrolyte of HEC.The preparation method is as follows, get the sulfuric acid solution of 198mL mass fraction 51.1%, adding 50g silicon dioxide quality mark is 40% Ludox under 300r/min stirs, the HEC aqueous solution that adds 74mL again, after treating that material adds, 1500r/min disperses (jitter time 30 minutes) to above-mentioned system.In the colloidal electrolyte that is obtained, the content of hydroxyethylcellulose is 0.009%(w/w), the silicon dioxide net content is 5%(w/w), the content of sulfuric acid is 1.28g/mL.
3. carry out flowability and viscosity test at once after the colloidal electrolyte preparation is finished; Treat that glue places its electrochemical properties of test and stability behind 24 hours gels.
Embodiment 5:
1. prepare mass fraction 0.05% hydroxyethyl cellulose aqueous solution
Fill in the dispersion bucket of deionized water of certain volume one and to add a certain amount of hydroxyethylcellulose powder, limit edged stirring at low speed is heightened speed high-speed stirred certain hour after adding, and leaves standstill to treat to change over to after foam disappears the volumetric flask constant volume and get final product.
2. the colloidal electrolyte of the HEC aqueous solution is not added in preparation;
Preparation does not contain the Ludox colloidal electrolyte of HEC.The preparation method is as follows, gets the sulfuric acid solution of 273mL mass fraction 40.6%, adds 50g silicon dioxide quality mark and be 40% Ludox under 300r/min stirs, treat that material adds after, 1500r/min disperses (jitter time 30 minutes) to above-mentioned system.
2. carry out flowability and viscosity test after the body electrolyte quota is finished at once; Treat that glue places its electrochemical properties of test and stability behind 24 hours gels.
The various embodiments described above different content HEC(w/w) The performance test results of colloidal electrolyte is shown in Fig. 1-8 time.
Fig. 1 fluidity testing is analyzed: add hydroxyethylcellulose and do not add hydroxyethylcellulose and relatively find, the colloidal electrolyte flowing time that adds hydroxyethylcellulose all is longer than and is not added hydroxyethylcellulose, and this mainly is that hydroxy ethyl fiber have thickening power and makes the mobile variation of glue.But be difficult for the aquation layering after taking all factors into consideration the perfusion of colloidal electrolyte and colloidal gel; when adding 0.003% hydroxyethylcellulose; can take into account simultaneously, neither the flowability to glue produces big influence, can fix again with the protecting colloid electrolyte and prevent the aquation layering.
Fig. 2 viscosity test is analyzed: contrast is added hydroxyethylcellulose and be found that with the viscosity test that does not add the colloidal electrolyte of hydroxyethylcellulose, the colloidal electrolyte viscosity of adding hydroxyethylcellulose all increases, and this also is the reason that hydroxy ethyl fiber have thickening power.The viscosity of colloidal electrolyte is with mobile directly related, and viscosity is low more, and flowing time is short approximately, and flowability is good more.Take into account colloidal electrolyte flowability and colloidal stability simultaneously, find to add 0.003% hydroxyethylcellulose, the viscosity of glue is minimum, and mobile best, this is consistent with the analysis result of Fig. 1.
Fig. 3 analyses the liquid measure test analysis: analysing the liquid measure test, mainly is to weigh the size that the electrolyte ability was fixed and stored to gel.It is more little to analyse liquid measure, illustrates that the colloid that forms is stable more, strong more to the fixing and storage effect of electrolyte.Find that by Fig. 3 when not adding hydroxyethylcellulose, it is lower that the Ludox colloidal electrolyte is analysed liquid measure, the fixed electrolyte performance is pretty good.When adding hydroxyethylcellulose in various colloidal electrolytes, with add 0.003% o'clock to analyse liquid measure minimum, though be higher than the liquid measure of analysing of Ludox slightly, but taking all factors into consideration the mobile of glue and generate the stability of colloid and prevent the effect of aquation layering, still is optimal selection when adding 0.003% hydroxyethylcellulose.
The strong test analysis of Fig. 4 glue: the size of colloid intensity is weighed from the degree of depth that equal height embeds gel with identical polyethylene pipe.It is generally acknowledged that insert depth is shallow more, the glue of gel is big more by force, and stability is good more.Find that by Fig. 4 when not adding hydroxyethylcellulose and be pure Ludox, the insert depth minimum illustrates that Ludox colloidal electrolyte gel strength is bigger.Add in the various colloidal electrolytes of hydroxyethylcellulose, more shallow to add 0.003% o'clock insert depth, though also be slightly greater than the insert depth of Ludox.0.003% hydroxyethylcellulose is added in this explanation can guarantee to take into account the thixotropy of gel on the strong basis of gel glue.This result with the evaluation stability of Fig. 3 is consistent.
Fig. 1 ~ 4 all are physical propertys of estimating glue or gel.As if tentatively, simple Ludox colloidal electrolyte more is better than having the colloidal electrolyte of additive, the glue physical property of adding 0.003% hydroxyethylcellulose is slightly excellent.But take all factors into consideration the electrochemical properties (analysis sees below) of colloidal electrolyte, simple Ludox colloidal electrolyte performance is not as the glue of an amount of additive.
Electrochemical impedance test analysis under Fig. 5 hydrogen-evolution overpotential: testing impedance is to weigh the difficulty that reaction takes place.Find that by Fig. 5 under the hydrogen-evolution overpotential, impedance spectrum presents the semicircle form, illustrates that evolving hydrogen reaction is the electric charge control procedure, the impedance semicircle is big more, illustrates that the charge transfer reaction is difficult more.When relatively finding to add 0.003% hydroxyethylcellulose, the impedance maximum of evolving hydrogen reaction illustrates that under this addition condition, colloidal electrolyte can suppress evolving hydrogen reaction well, can reduce the self discharge of battery.
Electrochemical impedance test analysis under Fig. 6 oxygen evolution potential: find that by Fig. 6 impedance spectrum also presents the semicircle form under the oxygen evolution potential, illustrates that oxygen evolution reaction is all the electric charge control procedure, same impedance semicircle is big more, illustrates that the charge transfer reaction is difficult more.When relatively finding to add 0.003% hydroxyethylcellulose; the impedance maximum of oxygen evolution reaction; illustrate under this addition condition; colloidal electrolyte can suppress oxygen evolution reaction well; the brown lead oxide corrosion product of the generation of simultaneous oxygen evolution reaction is also less; effectively protect plate Gate substrate Pb, suppressed its corrosion.
Fig. 7 cyclic voltammetric test analysis: find by Fig. 7, the hydroxyethylcellulose that adds different amounts exerts an influence hardly for the spike potential of lead with the redox peak of lead sulfate, and this illustrates that the interpolation of its ethyl cellulose does not influence the electrochemical reaction of active material and electrolyte.But different additions have certain influence to the peak current of reaction, when relatively finding to add 0.003% hydroxyethylcellulose, its plumbous redox electric current, redox electric weight with lead sulfate is all maximum, the hydroxyethylcellulose colloidal electrolyte of this explanation interpolation 0.003% can improve the colloid battery negative pole and discharge and recharge reaction, increase the negative discharge capacity, strengthen the negative pole charge acceptance, help suppressing the negative pole sulfation, improve the cycle life of colloid battery.
Electrochemical impedance test analysis under Fig. 8 Open Circuit Potential: find that by Fig. 8 impedance spectrum presents part semicircle form under the Open Circuit Potential, illustrate that impedance also is that the impedance semicircle is big more by charge transfer control under the Open Circuit Potential, illustrate that the charge transfer reaction is difficult more.Under the Open Circuit Potential, think the natural laying state of colloidal electrolyte, lead electrode is the spontaneous generation one deck lead sulfate film of meeting in electrolyte, and the lead sulfate film is considered to the alternative pellicle of one deck, can see through H +, OH -, if the lead sulfate that generates is few more, it is thin more then to hinder film, is beneficial to the transmission of electronics more.The lead sulfate of the more little generation of Open Circuit Potential impedance is minimum when adding 0.003% hydroxyethylcellulose by graph discovery, is beneficial to the transmission of the inner ion of electrolyte most.
Take all factors into consideration the physical property and the electrochemical properties of each electrolyte, to add the colloidal electrolyte best performance of 0.003% hydroxyethylcellulose preparation.

Claims (10)

1. a lead acid accumulator colloidal electrolyte is characterized in that described electrolyte is the Ludox electrolyte of gel with the Ludox, and wherein contains hydroxyethylcellulose.
2. electrolyte as claimed in claim 1 is characterized in that the mass fraction of described hydroxyethylcellulose in electrolyte is 0.001% ~ 0.009%.
3. electrolyte as claimed in claim 2 is characterized in that the mass fraction of described hydroxyethylcellulose in electrolyte is 0.003%.
4. electrolyte as claimed in claim 2 is characterized in that containing silicon dioxide and sulfuric acid in the described Ludox electrolyte, and the mass fraction of silicon dioxide net content in electrolyte is 4 ~ 6%; The density of sulfuric acid in electrolyte is 1.26 ~ 1.32g/mL.
5. the preparation method of electrolyte as claimed in claim 1 is characterized in that may further comprise the steps:
(1) hydroxyethyl cellulose aqueous solution of preparation mass fraction 0.05% ~ 0.5%;
(2) silicon dioxide is configured as Ludox or employing finished silicon colloidal sol, joins in the sulfuric acid solution, stir;
(3) hydroxyethyl cellulose aqueous solution with step (1) joins in the solution of step (2) acquisition, and disperses.
6. the preparation method of electrolyte as claimed in claim 5 is characterized in that the concentration of the described sulfuric acid solution of step (2) is 40.6% ~ 51.1%, and the mass fraction of silicon dioxide is 39.5% ~ 40.5% in the Ludox.
7. the preparation method of electrolyte as claimed in claim 5 is characterized in that the described stirring of step (2) is a stirring at low speed, and rotating speed is 200 ~ 500 r/min.
8. the preparation method of electrolyte as claimed in claim 7 is characterized in that described rotating speed is 300r/min.
9. the preparation method of electrolyte as claimed in claim 5 is characterized in that the described high speed dispersion that is separated into of step (3), and rotating speed is 1400 ~ 1600r/min, and jitter time is 20 ~ 40min.
10. the preparation method of electrolyte as claimed in claim 9, the rotating speed that it is characterized in that step is 1500r/min, jitter time is 30min.
CN2011101237519A 2011-05-13 2011-05-13 Colloid electrolyte for lead-acid battery and preparation method thereof Pending CN102208690A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102522596A (en) * 2011-12-30 2012-06-27 山东宏艺电源技术有限公司 Lead-acid storage battery collide electrolyte, preparation method thereof and lead-acid storage battery
CN103594738A (en) * 2013-12-12 2014-02-19 湖南丰日电源电气股份有限公司 High-temperature valve regulated sealed lead-acid storage battery
CN105514505A (en) * 2016-01-22 2016-04-20 英德奥克莱电源有限公司 Deep circulating valve controlled lead-acid battery and preparation method thereof
CN112510214A (en) * 2020-12-08 2021-03-16 英德奥克莱电源有限公司 Lead-acid storage battery with excellent starting performance and preparation method thereof
CN113285183A (en) * 2021-04-16 2021-08-20 安徽超威电源有限公司 Acid charging method for prolonging cycle life of valve-regulated lead-acid storage battery for power
CN113555611A (en) * 2021-06-30 2021-10-26 河南超威电源有限公司 Nano-colloid electrolyte for lead-acid battery and preparation method thereof
CN114374001A (en) * 2021-12-31 2022-04-19 江苏理士电池有限公司 Novel lead-acid storage battery colloidal electrolyte and preparation method thereof

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CN1702900A (en) * 2005-06-02 2005-11-30 胡延强 Solid storage battery having solid and liquid phase electrolyte
CN102024992A (en) * 2010-11-02 2011-04-20 江苏双登集团有限公司 Lead-acid storage battery colloidal electrolyte and preparation method

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Publication number Priority date Publication date Assignee Title
CN1702900A (en) * 2005-06-02 2005-11-30 胡延强 Solid storage battery having solid and liquid phase electrolyte
CN102024992A (en) * 2010-11-02 2011-04-20 江苏双登集团有限公司 Lead-acid storage battery colloidal electrolyte and preparation method

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102522596A (en) * 2011-12-30 2012-06-27 山东宏艺电源技术有限公司 Lead-acid storage battery collide electrolyte, preparation method thereof and lead-acid storage battery
CN102522596B (en) * 2011-12-30 2014-05-07 山东宏艺电源技术有限公司 Lead-acid storage battery collide electrolyte, preparation method thereof and lead-acid storage battery
CN103594738A (en) * 2013-12-12 2014-02-19 湖南丰日电源电气股份有限公司 High-temperature valve regulated sealed lead-acid storage battery
CN103594738B (en) * 2013-12-12 2015-12-02 湖南丰日电源电气股份有限公司 A kind of high temperature valve controlled sealed lead-acid accumulator
CN105514505A (en) * 2016-01-22 2016-04-20 英德奥克莱电源有限公司 Deep circulating valve controlled lead-acid battery and preparation method thereof
CN112510214A (en) * 2020-12-08 2021-03-16 英德奥克莱电源有限公司 Lead-acid storage battery with excellent starting performance and preparation method thereof
CN113285183A (en) * 2021-04-16 2021-08-20 安徽超威电源有限公司 Acid charging method for prolonging cycle life of valve-regulated lead-acid storage battery for power
CN113555611A (en) * 2021-06-30 2021-10-26 河南超威电源有限公司 Nano-colloid electrolyte for lead-acid battery and preparation method thereof
CN114374001A (en) * 2021-12-31 2022-04-19 江苏理士电池有限公司 Novel lead-acid storage battery colloidal electrolyte and preparation method thereof
CN114374001B (en) * 2021-12-31 2023-10-27 江苏理士电池有限公司 Novel lead-acid storage battery colloid electrolyte and preparation method thereof

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Application publication date: 20111005